Functionalized resin having a polar linker

ABSTRACT

Polar silane linkers are provided that attach to resins to form silane-functionalized resins. The functionalized resins can be bound to hydroxyl groups on the surface of silica particles to improve the dispersibility of the silica particles in rubber mixtures. Further disclosed are synthetic routes to provide the silane-functionalized resins, as well as various uses and end products that benefit from the unexpected properties of the silane-functionalized resins. Silane-functionalized resins impart remarkable properties on various rubber compositions, such as tires, belts, hoses, brakes, and the like. Automobile tires incorporating the silane-functionalized resins are shown to possess excellent results in balancing the properties of rolling resistance, tire wear, and wet braking performance.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to and the benefit of U.S. ProvisionalPatent Application Ser. No. 62/483,835, filed Apr. 10, 2017, andInternational Patent Application No. PCT/US2018/26752, filed Apr. 9,2018, both of which are entitled, “Functionalized Resin Having A PolarLinker,” which applications are incorporated herein by reference intheir entirety.

PARTIES TO A JOINT RESEARCH AGREEMENT

This disclosure was created pursuant to a joint development agreementbetween Eastman Chemical Company, a Delaware corporation, andContinental Reifen Deutschland GmbH, a German corporation, that was ineffect on or before the date the claimed invention was made, and theclaimed invention was made as a result of activities undertaken withinthe scope of the joint development agreement.

FIELD

Silane functionalized resins are disclosed that contain a polar silanelinker as the functionalizing group. The functionalized resins can bebound to hydroxyl groups on the surface of silica particles to improvethe dispersibility of the silica particles in rubber mixtures that alterthe viscoelastic and performance properties of the cured rubbercompounds. Further, synthetic routes to prepare the polar or amphiphilicsilane linker and to attach the linker to a resin are disclosed, as wellas synthetic routes to copolymerize a silane functionalized monomer.Various uses and end products that impart excellent performance due tothe unexpected properties of these functionalized resins are alsodisclosed.

BACKGROUND

Rubber mixtures typically contain filler material to improve technicalrequirements of the tire compositions, such as high wear resistance, lowrolling resistance, or wet grip. However, the technical requirements areoften in conflict with each other, as, for example, a change incomposition to lower rolling resistance of a tire can in turn decreasethe wet grip.

Silica is a widely-used filler material for rubber mixtures. Inparticular, silica is often included in rubber mixtures for vehicletires. However, the surface of silica particles is hydrophilic due tothe presence of polar hydroxyl groups, whereas the rubber material in atire is typically more hydrophobic, which can make it difficult todisperse the silica particles in the rubber mixture during themanufacture of the tire.

Current resin technology for tires uses high glass transition resins tomodify the rubber glass transition temperature Tg and viscoelasticproperties to improve wet grip and rolling resistance performancebalance. The wet grip performance must be balanced with other tireproperties including rolling resistance and wear that are affected bythe introduction of resin.

Lately, resins have increasingly been used in rubber mixtures forvehicle tire applications, in particular in rubber mixtures for tiretreads. U.S. Patent Application Publication No. 2016/0222197 disclosestire treads containing resins in amounts exceeding 50 phr. A goodcompatibility between rubber and resin is a prerequisite for achievinghigh resin loadings in the polymer matrix.

Commercially available resins are not functionalized to achieve aspecific attachment to the surface of the filler material. Thus,commercially available resins are distributed throughout the polymermatrix and do not target the silica interface with rubber.

International Patent Application Publication No. WO 2015/153055discloses dicyclopentadiene (DCPD)-based polymers that arefunctionalized with a functional group of Formula P—S—X, where S is analiphatic or aromatic spacer, P is a polymer backbone, and X is asilane. However, DCPD-based resins exhibit a reduced solubility in atleast some rubber mixtures for tires.

Further, from U.S. Patent Application Publication No. 2013/0296475 it isknown to provide thermoplastic polymers with a terminal functionalgroup. In some of the examples therein resins with a relatively highmolecular weight of Mn (number average molecular weight) of 2,500 to10,000 g/mol are used. However, with increasing molecular weight of ahydrocarbon resin, the compatibility with the polymer matrix maydecrease.

Thus, disclosed are functionalized resins that are employed asprocessing aids or are used to prevent damping or energy dissipationeffects provided by unbound resin in a vehicle tire. Specifically, thedamping properties of the rubber mixtures can be modified in asite-specific manner. The functionalized resins disclosed herein attachto the surface of a filler material, preferably silica, through areactive group, preferably a reactive silane group that is bound to apolar linker. Surprisingly, the functionalized resin can efficientlymodify the polymer-filler interface, such that the viscoelasticproperties of the rubber mixture are improved. Conflicting technicalrequirements of the tire compositions, such as improved wet grip andlower rolling resistance can be effectively resolved at a higher level.

SUMMARY

Provided herein are resin compositions functionalized with silane. Ithas been discovered that functionalization of resins with silane asdisclosed herein confer superior unexpected properties, such thatproducts, such as rubber products, adhesive, tires, belts, gaskets,hoses, and the like, possess superior properties as compared to similarproducts without the disclosed functionalized resins. Disclosed are alsomethods of obtaining, manufacturing, synthesizing, or creating suchresins, as well as various end-products incorporating the disclosedfunctionalized resins.

The resin compositions have the general structure of Formula I, where“resin” represents the backbone of the resin:

resin-[Z_(k)—X_(n)—R¹—(CH₂)_(m)—Si(R²)_(p)]_(q)  (I)

wherein Z is an aromatic group or an aliphatic group, optionallycomprising a heteroatom;

wherein X is a linker comprising a heteroatom selected from sulfur,oxygen, nitrogen, a carbonyl group, or a combination thereof;

wherein R¹ comprises one or more of an aliphatic and/or aromatic C₁ toC₁₈ and/or a linkage group comprising a heteroatom;

wherein each R² is the same or different and is independently selectedfrom a C₁ to C₁₈ alkoxy, aryloxy, alkyl, aryl, or H, or OH, and isoptionally branched, and wherein at least one R² is C₁ to C₁₈ alkoxy,aryloxy, or H, or OH;

wherein q is an integer from of at least 1;

wherein k is an integer of 0 or 1;

wherein n is an integer from 1 to 10;

wherein m is an integer from 0 to 10; and,

wherein p is 1, 2, or 3.

Disclosed are embodiments directed to methods, modes, processes, andprocedures for synthesizing, manufacturing, producing, or otherwisegenerating the functionalized resins described by Formula I. Suchprocesses include various steps including, but not limited to Step (a)that is directed to converting a phenol-modified resin having Formula(II): resin-Z_(k)—OH, to an acid-modified resin having Formula (III):resin-Z_(k)—X_(n)—COOH. In this optional step, resin, Z, k, X, and n areas defined above. Another step, Step (b), involved in the process forgenerating the described functionalized resins includes reacting theacid-modified resin of Formula (III) with a silane coupling agent,optionally in the presence of an activation agent, and optionally in thepresence of a catalyst. In one embodiment, the acid modified resinhaving Formula (III) is obtained by polymerizing or co-polymerizing oneor more monomers having a carboxylic acid functional group or bypolymerization in the presence of a modifier comprising a carboxylicacid functional group, such as a free radical initiator or a chainterminator.

In one embodiment of the described processes for producing the describedfunctionalized resins, the optional Step (a) also involves reacting thephenol-modified resin of Formula (II) with a cyclic acid anhydride ofFormula (IV) or a terminal halogen-substituted straight-chain carboxylicacid of Formula (V), where this reaction is optionally performed in thepresence of a catalyst:

In such methods, R³ is independently selected from substituted andunsubstituted, saturated, unsaturated, and polyunsaturated C₁-C₈ alkyl,substituted and unsubstituted C₆-C₂₀ carbocyclic aryl, and substitutedand unsubstituted C₄-C₂₀ heterocyclic. Also, in such methods, theheteroatoms are one or more of sulfur, nitrogen, and oxygen, Y is ahalogen atom; and n is an integer from 1-6. In such methods, the cyclicacid anhydride of Formula (IV) is selected from malonic anhydride,succinic anhydride, methylsuccinic anhydride, glutaric anhydride, adipicanhydride, pimelic anhydride, phthalic anhydride, trimellitic anhydride,and maleic anhydride.

In another embodiment of the disclosed processes for producing thefunctionalized resin described by Formula (I), the process is optionallyperformed with no solvent or in an inert solvent. In such embodiments,the inert solvent is one or more of a cyclic ether solvent, an acyclicether solvent, a ketone solvent, aromatic hydrocarbons, aliphaticsaturated hydrocarbons, aliphatic unsaturated hydrocarbons, alicyclicsaturated hydrocarbons, alicyclic unsaturated hydrocarbons, halogenatedhydrocarbons, and polar aprotic solvents.

Further embodiments of the disclosed processes involve a Step (b) thatis performed by reaction with a silane coupling agent having Formula(VI): W—(CH₂)_(m)—Si(R²)_(p), where m, R², and p as defined above, andwhere W is independently selected from the group consisting of: amine,diamine, thiol, isocyanate, epoxide, alkene, and halogen.

The described synthesis methods, in some embodiments, are performed at atemperature of about 0° C. to about 300° C., about 100° C. to about 250°C., or about 150° C. to about 250° C. In embodiments employing acatalyst, the catalyst is one or more of quaternary ammonium salts,quaternary phosphonium salts, iodide salts, triphenylphosphine,4-dimethylaminopyridine, alkaline, Lewis acids, and Bronsted acids.

In a further embodiment of the disclosed methods of synthesizing thedescribed functionalized resins, the method involves synthesis of asilane functionalized resin having Formula (I), as defined above, thatinvolves contacting a phenol modified resin having Formula (II):resin-Z_(k)—OH with a silane coupling agent having Formula (VI):W—(CH₂)_(m)—Si(R²)_(p), where resin, Z, k, W, m, R², and p are asdefined above. Such methods are optionally performed in the presence ofa catalyst. Such methods are performed in no solvent or in an inertsolvent, where the inert solvent is at least one of a cyclic ethersolvent, an acyclic ether solvent, a ketone solvent, aromatichydrocarbons, aliphatic saturated hydrocarbons, aliphatic unsaturatedhydrocarbons, alicyclic saturated hydrocarbons, alicyclic unsaturatedhydrocarbons, halogenated hydrocarbons, and polar aprotic solvents. Insuch embodiments, the various steps of the method of synthesis of thedescribed are performed at a temperature of about 0° C. to about 300°C., about 100° C. to about 250° C., or about 150° C. to about 250° C. Insuch embodiments, the catalyst is one or more of quaternary ammoniumsalts, quaternary phosphonium salts, iodide salts, triphenylphosphine,4-dimethylaminopyridine, alkaline, Lewis acids, and Bronsted acids.

Also provided are embodiments which include a polymerization process toproduce a silane functionalized resin having Formula (I), as definedabove, which comprises heating a mixture of monomers comprising: (i) oneor more alkyl, aryl, and/or aralkyl acrylates/methacrylates, (ii) atleast one trialkoxysilyl-functionalized alkyl, aryl, and/or aralkylacrylate/methacrylate, (iii) optionally one or more vinyl ester and/orstyrene or alkyl-substituted styrene, and (iv) optionally an inertsolvent. In such embodiments, heating is performed in the presence of asubstance that forms free radicals when heated, and the mixturetemperature is raised sufficiently to cause the substance to decomposeand initiate co-polymerization of the monomer mixture.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will now be described with reference to the drawings. Theaccompanying drawings, which are incorporated in and constitute a partof this specification, illustrate certain embodiments, and together withthe written description, serve to explain certain principles of theconstructs and methods disclosed herein.

FIG. 1A through FIG. 1M show aspects of synthetic routes andarchitectures for silane-functionalizing resins. FIG. 1A shows synthesisof pendant silane-containing resins via acetoxystyrenefunctionalization. FIG. 1B shows synthesis of end-cappedsilane-containing resin via phenol functionalization. FIG. 1C showssynthesis of pendant silane-containing resins via phenolfunctionalization with anhydride silane. FIG. 1D shows synthesis ofpendant silane-containing resin via succinic anhydride grafting ontoresin. FIG. 1E shows synthesis of pendant silane-containing resin viafree radical copolymerization. FIG. 1F shows various architectureembodiments surrounding the variable group Z. FIG. 1G shows synthesis ofend-capped silane-containing resins by phenol functionalization throughsuccinic anhydride. FIG. 1H shows synthesis of end-cappedsilane-containing resins by phenol functionalization with chloro-silane.FIG. 1I shows synthesis of pendant silane-containing resins bycopolymerization of isobornylmethacrylate and3-(trimethoxysilyl)propylmethacrylate. FIG. 1J shows synthesis ofend-capped silane-containing resins via phenol functionalization withglycidoxy silane. FIG. 1K shows synthesis of end-cappedsilane-containing resin via acid functionalization with glycidoxysilane. FIG. 1L shows synthesis of end-capped silane-containing resinvia phenol functionalization with glycidoxy silane. FIG. 1M showssynthesis of end-capped silane-containing resin via phenolfunctionalization with phthalic anhydride and glycidoxy silane.

FIG. 2A shows schematically prior art resin that simply intercalatesinto polymer matrix. FIG. 2B shows schematically the binding of afunctionalized resin to the surface of a silica particle SiO₂.

FIG. 3 shows a representative Fourier transform-infrared (FT-IR)spectrum for the functionalized resin synthesis product of Step 1A, thesynthesis of a pendant phenol-functionalized resin from acetoxystyrenedeprotection as described in Example 1.1.

FIG. 4 shows a representative thermogravimetric analysis (TGA) trace forthe functionalized resin synthesis product of Step 1A, the synthesis ofa pendant phenol-functionalized resin from acetoxystyrene deprotectionas described in Example 1.1.

FIG. 5 shows a representative differential scanning calorimetry (DSC)trace for the functionalized resin synthesis product of Step 1A, thesynthesis of a pendant phenol-functionalized resin from acetoxystyrenedeprotection as described in Example 1.1.

FIG. 6 shows a representative FT-IR spectrum for the functionalizedresin synthesis product of Step 1B, the synthesis of a pendantcarboxylic acid-functionalized resin from phenol group functionalizationas described in Example 1.1.

FIG. 7 shows a representative TGA trace for the functionalized resinsynthesis product of Step 1B, the synthesis of a pendant carboxylicacid-functionalized resin from phenol group functionalization asdescribed in Example 1.1.

FIG. 8 shows a representative DSC trace for the functionalized resinsynthesis product of Step 1B, the synthesis of a pendant carboxylicacid-functionalized resin from phenol group functionalization asdescribed in Example 1.1.

FIG. 9 shows a representative FT-IR spectrum for the functionalizedresin synthesis product of Step 1C, the synthesis of a pendantsilane-functionalized resin from a carboxylic acid groupfunctionalization as described in Example 1.1.

FIG. 10 shows a representative TGA trace for the functionalized resinsynthesis product of Step 1C, the synthesis of a pendantsilane-functionalized resin from a carboxylic acid groupfunctionalization as described in Example 1.1.

FIG. 11 shows a representative DSC trace for the functionalized resinsynthesis product of Step 1C, the synthesis of a pendantsilane-functionalized resin from a carboxylic acid groupfunctionalization as described in Example 1.1.

FIG. 12 shows a representative gel permeation chromatography (GPC) tracefor the functionalized resin synthesis product of Step 1C, the synthesisof a pendant silane-functionalized resin from a carboxylic acid groupfunctionalization as described in Example 1.1.

FIG. 13 shows a representative FT-IR spectrum for the functionalizedresin synthesis product of Step 2A, the synthesis of an end-cappedcarboxylic acid-functionalized resin from the phenol groupfunctionalization as described in Example 1.2.

FIG. 14 shows a representative TGA trace for the functionalized resinsynthesis product of Step 2A, the synthesis of an end-capped carboxylicacid-functionalized resin from the phenol group functionalization asdescribed in Example 1.2.

FIG. 15 shows a representative DSC trace for the functionalized resinsynthesis product of Step 2A, the synthesis of an end-capped carboxylicacid-functionalized resin from the phenol group functionalization asdescribed in Example 1.2.

FIG. 16 shows a representative FT-IR spectrum for the functionalizedresin synthesis product of Step 2B, the synthesis of an end-cappedsilane-functionalized resin from the carboxylic acid groupfunctionalization as described in Example 1.2.

FIG. 17 shows a representative TGA trace for the functionalized resinsynthesis product of Step 2B, the synthesis of an end-cappedsilane-functionalized resin from the carboxylic acid groupfunctionalization as described in Example 1.2.

FIG. 18 shows a representative DSC trace for the functionalized resinsynthesis product of Step 2B, the synthesis of an end-cappedsilane-functionalized resin from the carboxylic acid groupfunctionalization as described in Example 1.2.

FIG. 19 shows a representative GPC trace for the functionalized resinsynthesis product of Step 2B, the synthesis of an end-cappedsilane-functionalized resin from the carboxylic acid groupfunctionalization as described in Example 1.2.

FIG. 20 shows a representative ¹³C nuclear magnetic resonance (NMR)trace for the functionalized resin synthesis product of Step 2B, thesynthesis of an end-capped silane-functionalized resin from thecarboxylic acid group functionalization as described in Example 1.2.

FIG. 21 shows a representative ²⁹Si NMR trace for the functionalizedresin synthesis product of Step 2B, the synthesis of an end-cappedsilane-functionalized resin from the carboxylic acid groupfunctionalization as described in Example 1.2.

FIG. 22 shows a representative FT-IR spectrum for the functionalizedresin synthesis product of Step 3B, the synthesis of a pendantsilane-functionalized resin from acetoxystyrene deprotection asdescribed in Example 1.3.

FIG. 23 shows a representative TGA trace for the functionalized resinsynthesis product of Step 3B, the synthesis of a pendantsilane-functionalized resin from acetoxystyrene deprotection asdescribed in Example 1.3.

FIG. 24 shows a representative DSC trace for the functionalized resinsynthesis product of Step 3B, the synthesis of a pendantsilane-functionalized resin from acetoxystyrene deprotection asdescribed in Example 1.3.

FIG. 25 shows a representative FT-IR spectrum for the functionalizedresin synthesis product of Step 4A, the synthesis of a pendantcarboxylic acid-functionalized resin from a phenol modification withanhydride silane as described in Example 1.4.

FIG. 26 shows a representative TGA trace for the functionalized resinsynthesis product of Step 4A, the synthesis of a pendant carboxylicacid-functionalized resin from a phenol modification with anhydridesilane as described in Example 1.4.

FIG. 27 shows a representative DSC trace for the functionalized resinsynthesis product of Step 4A, the synthesis of a pendant carboxylicacid-functionalized resin from a phenol modification with anhydridesilane as described in Example 1.4.

FIG. 28 shows a representative GPC trace for the functionalized resinsynthesis product of Step 4A, the synthesis of a pendant carboxylicacid-functionalized resin from a phenol modification with anhydridesilane as described in Example 1.4.

FIG. 29 shows a representative FT-IR spectrum for the functionalizedresin synthesis product of Step 4B, the synthesis of a pendantsilane-functionalized resin derived from grafting succinic anhydrideonto Kristalex™ 3085 as described in Example 1.4.

FIG. 30 shows a representative TGA trace for the functionalized resinsynthesis product of Step 4B, the synthesis of a pendantsilane-functionalized resin derived from grafting succinic anhydrideonto Kristalex™ 3085 as described in Example 1.4.

FIG. 31 shows a representative DSC trace for the functionalized resinsynthesis product of Step 4B, the synthesis of a pendantsilane-functionalized resin derived from grafting succinic anhydrideonto Kristalex™ 3085 as described in Example 1.4.

FIG. 32 shows a representative GPC trace for the functionalized resinsynthesis product of Step 4B, the synthesis of a pendantsilane-functionalized resin derived from grafting succinic anhydrideonto Kristalex™ 3085 as described in Example 1.4.

FIG. 33 shows a representative ¹H NMR trace for the functionalized resinsynthesis product of Step 4B, the synthesis of a pendantsilane-functionalized resin derived from grafting succinic anhydrideonto Kristalex™ 3085 as described in Example 1.4.

FIG. 34 shows a representative ¹³C NMR trace for the functionalizedresin synthesis product of Step 4B, the synthesis of a pendantsilane-functionalized resin derived from grafting succinic anhydrideonto Kristalex™ 3085 (Eastman Chemical, Ltd., Kingsport, Tenn., US) asdescribed in Example 1.4.

FIG. 35 shows a representative ²⁹Si NMR trace for the functionalizedresin synthesis product of Step 4B, the synthesis of a pendantsilane-functionalized resin derived from grafting succinic anhydrideonto Kristalex™ 3085 as described in Example 1.4.

FIG. 36 shows a representative GPC trace for the functionalized resinsynthesis product of Step 5A, the synthesis of a pendantsilane-functionalized resin from a free radical copolymerization withmethacrylate silane as described in Example 1.5.

FIG. 37 shows a representative ¹H NMR trace for the functionalized resinsynthesis product of Step 5A, the synthesis of a pendantsilane-functionalized resin from a free radical copolymerization withmethacrylate silane as described in Example 1.5.

FIG. 38 shows a representative FT-IR spectrum for the functionalizedresin synthesis product achieved by phenol functionalization throughsuccinic anhydride, as described in Example 1.6.

FIG. 39 shows a representative TGA trace for the functionalized resinsynthesis product achieved by phenol functionalization through succinicanhydride as described in Example 1.6.

FIG. 40 shows a representative DSC trace for the functionalized resinsynthesis product achieved by phenol functionalization through succinicanhydride as described in Example 1.6.

FIG. 41 shows a representative GPC trace for the functionalized resinsynthesis product achieved by phenol functionalization through succinicanhydride as described in Example 1.6.

FIG. 42 shows a representative ²⁹Si NMR trace for end-cappedsilane-containing resins produced by phenol functionalization withchloro-silane, as described in Example 1.7.

FIG. 43 shows a representative ¹H-NMR trace for pendantsilane-containing resins synthesized by copolymerization ofisobornylmethacrylate and 3-(trimethoxysilyl)propyl-methacrylate, asdescribed in Example 1.8.

FIG. 44 shows a representative DSC trace for pendant silane-containingresins synthesized by copolymerization of isobornylmethacrylate and3-(trimethoxysilyl)propyl-methacrylate, as described in Example 1.8.

FIG. 45 shows a representative ²⁹Si-NMR trace for pendantsilane-containing resins synthesized by copolymerization ofisobornylmethacrylate and 3-(trimethoxysilyl)propyl-methacrylate, asdescribed in Example 1.8.

FIG. 46 shows a representative IR trace for pendant silane-containingresins synthesized by copolymerization of isobornylmethacrylate and3-(trimethoxysilyl)propyl-methacrylate, as described in Example 1.8.

FIG. 47 shows a representative TGA trace obtained of an end-cappedsilane-containing resin end product obtained by phenol functionalizationwith glycidoxy silane, as described in Example 1.9.

FIG. 48 shows a representative DSC trace obtained of an end-cappedsilane-containing resin end product obtained by phenol functionalizationwith glycidoxy silane, as described in Example 1.9.

FIG. 49 shows a representative ¹H-NMR trace obtained of an end-cappedsilane-containing resin end product obtained by phenol functionalizationwith glycidoxy silane, as described in Example 1.9.

FIG. 50 shows a representative GPC trace obtained of an end-cappedsilane-containing resin end product obtained by phenol functionalizationwith glycidoxy silane, as described in Example 1.9.

FIG. 51 shows a representative GPC trace obtained of an end-cappedsilane-containing resin obtained by acid functionalization withglycidoxy silane, as described in Example 1.10.

FIG. 52 shows a representative ¹H-NMR trace obtained of an end-cappedsilane-containing resin obtained by acid functionalization withglycidoxy silane, as described in Example 1.10.

FIG. 53 shows a representative TGA trace obtained of an end-cappedsilane-containing resin obtained by acid functionalization withglycidoxy silane, as described in Example 1.10.

FIG. 54 shows a representative DSC trace of an end-cappedsilane-containing resin obtained by phenol functionalization withglycidoxy silane, as described in Example 1.11.

FIG. 55 shows a representative GPC trace of an end-cappedsilane-containing resin obtained by phenol functionalization withglycidoxy silane, as described in Example 1.11.

FIG. 56 shows a representative ¹H-NMR trace of an end-cappedsilane-containing resin obtained by phenol functionalization withglycidoxy silane, as described in Example 1.11.

FIG. 57 shows a representative TGA trace of an end-cappedsilane-containing resin obtained by phenol functionalization withglycidoxy silane, as described in Example 1.11.

FIG. 58 shows a representative ¹H-NMR trace of an end-cappedsilane-containing resin obtained by phenol functionalization withphthalic anhydride and glycidoxy silane, as described in Example 1.12.FIG. 59 shows a representative GPC trace of an end-cappedsilane-containing resin obtained by phenol functionalization withphthalic anhydride and glycidoxy silane, as described in Example 1.12.

FIG. 60 shows a graph of resilience vs. Shore A hardness for each of thesamples tested in Example 3.

DETAILED DESCRIPTION

It is to be understood that the following detailed description isprovided to give the reader a fuller understanding of certainembodiments, features, and details of aspects of the invention, andshould not be interpreted as a limitation of the scope of the invention.

Definitions

Certain terms used throughout this disclosure are defined hereinbelow sothat the present invention may be more readily understood. Additionaldefinitions are set forth throughout the disclosure.

Each term that is not explicitly defined in the present application isto be understood to have a meaning that is commonly accepted by thoseskilled in the art. If the construction of a term would render itmeaningless or essentially meaningless in its context, the term'sdefinition should be taken from a standard dictionary.

The use of numerical values in the various ranges specified herein,unless otherwise expressly indicated otherwise, are considered to beapproximations as though the minimum and maximum values within thestated ranges were both preceded by the word “about.” In this context,the term “about” is meant to encompass the stated value+a deviation of1%, 2%, 3%, 4%, or not more than 5% of the stated value. In this manner,slight variations above and below the stated ranges can be used toachieve substantially the same results as the values within the ranges.In addition, the disclosure of these ranges is intended as a continuousrange including every value between the minimum and maximum values.

Unless otherwise indicated, % solids or weight % (wt %) are stated inreference to the total weight of a specific Formulation, emulsion, orsolution.

Unless otherwise indicated, the terms “polymer” and “resin” mean thesame thing, and include both homopolymers having the same recurring unitalong the backbone, as well as copolymers having two or more differentrecurring units along the backbone. Such polymers or resins include butare not limited to, materials prepared by either condensation, cationic,anionic, Ziegler-Natta, reversible addition-fragmentation chain-transfer(RAFT), or free radical polymerization.

The term “comprising” (and its grammatical variations) as used herein isused in the inclusive sense of “having” or “including” and not in theexclusive sense of “consisting only of.”

The terms “a” and “the” as used herein are understood to encompass oneor more of the components, i.e., the plural as well as the singular.

The stated “phr” means parts per hundred parts of rubber by weight, andis used in this specification to mean the conventional stated amount inthe rubber industry for blend recipes. The dosage of the parts by weightof the individual substances in this context is always based on 100parts by weight of the total weight of all the rubbers present in theblend. The abovementioned resins are not considered to be a rubber inthe context of this disclosure.

A “thermoplastic polymer” refers to a polymer that has no covalentlycrosslinked sites between individual polymer macromolecules and becomesliquid, pliable, or moldable above a specific temperature, and then itreturns to a solid state upon cooling. In many instances, thethermoplastic polymers are also soluble in appropriate organic solventmedia.

Unless otherwise indicated, the term “mol %” when used in reference torecurring units in polymers, refers to either the nominal (theoretical)amount of a recurring unit based on the molecular weight ofethylenically unsaturated polymerizable monomer used in thepolymerization process, or to the actual amount of recurring unit in theresulting polymer as determined using suitable analytical techniques andequipment.

The term “vulcanized” as used herein means subjecting a chemicalcomposition, such as a polymer, for example an elastomeric and/orthermoplastic polymer composition, to a chemical process includingaddition of sulfur or other similar curatives, activators, and/oraccelerators at a high temperature. (See, for example, WO 2007/033720,WO 2008/083242, and PCT/EP2004/052743). The curatives and acceleratorsact to form crosslinks, or chemical bridges, between individual polymerchains. Curing agents collectively refer to sulfur vulcanizing agentsand vulcanization accelerators. Suitable sulfur vulcanizing agentsinclude, for example, elemental sulfur (free sulfur) or sulfur donatingvulcanizing agents that make sulfur available for vulcanization at atemperature of about 140° C. to about 190° C. Suitable examples ofsulfur donating vulcanizing agents include amino disulfide, polymericpolysulfide, and sulfur olefin adducts. The polymer compositionsdescribed herein that are capable of being vulcanized can in someembodiments also include one or more vulcanizing accelerators.Vulcanizing accelerators control the time and/or temperature requiredfor vulcanization and affect the properties of the vulcanizate.Vulcanization accelerators include primary accelerators and secondaryaccelerators. Suitable accelerators include, for example, one or more ofmercapto benzothiazole, tetramethyl thiuram disulfide, benzothiazoledisulfide, diphenyl guanidine, zinc dithiocarbamate, alkylphenoldisulfide, zinc butyl xanthate,N-dicyclohexyl-2-benzothiazolesulfenamide, N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene benzothiazole-2-sulfenamide, N,N-diphenylthiourea, dithiocarbamyl sulfenamide, N,N-diisopropylbenzothiozole-2-sulfenamide, zinc-2-mercapto toluimidazole, dithiobis(N-methyl piperazine), dithio bis(N-beta-hydroxy ethyl piperazine),and dithio bis(dibenzyl amine). Other vulcanizing accelerators include,for example, thiuram, and/or morpholine derivatives. Further, vulcanizedcompounds also in some embodiments include one or more silane couplingagents such as, for example, bifunctional organosilanes possessing atleast one alkoxy, cycloalkoxy, or phenoxy group on the silicon atom as aleaving group, and as the other functionality, having a group that canoptionally undergo a chemical reaction with the double bonds of thepolymer after splitting. The latter group may, for example, constitutethe following chemical groups: SCN, —SH, —NH2 or -Sx- (where x is from 2to 8). Thus, vulcanizates, i.e. mixtures to be vulcanized include insome embodiments various combinations of exemplary silane couplingagents such as 3-mercaptopropyltriethoxysilane,3-thiocyanato-propyl-trimethoxysilane, or3,3′-bis(triethoxysilylpropyl)-polysulfide with 2 to 8 sulfur atoms suchas, for example, 3,3′-bis(triethoxysilylpropyl)tetrasulfide (TESPT), thecorresponding disulfide (TESPD), or mixtures of the sulfides with 1 to 8sulfur atoms having a differing content of the various sulfides, asdescribed in further detail below.

“Weight-average molecular weight (M_(w))” is determined using gelpermeation chromatography (GPC). Values reported herein are reported aspolystyrene equivalent weights.

The term “Mn” when used herein means the number average molecular weightin g/mol, i.e. the statistical average molecular weight of all polymerchains in the sample, or the total weight of all the molecules in apolymer sample divided by the total number of molecules present.

The term “Mz” when used herein means the z-average molecular weight ing/mol and is determined typically by sedimentation equilibrium(ultracentrifugation) and light scattering. Here Mz is determined by gelpermeation chromatography (GPC) according to methods described below. Mzis the thermodynamic equilibrium position of a polymer where the polymermolecule becomes distributed according to its molecular size. This valueis used in some instances as an indication of the high molecular weighttail in the thermoplastic resin.

“Glass transition temperature (Tg)” is a second order transition and isthe temperature range at which amorphous material reversibly changesfrom a hard, rigid, or “glassy” solid state to a more pliable,compliant, or “rubbery” viscous state, and is measured in degreesCelsius or degrees Fahrenheit. Tg is not the same as meltingtemperature. Tg can be determined using Differential Scanningcalorimetry (DSC) as disclosed below at Example 2.

The terms “end-capped” and “terminally capped” are used interchangeablyherein to refer to a terminal or end point of a polymer having a silanegroup located at the end point or terminus of the polymer. Silanemolecules of Formula I can be located at the end point or terminus of aresin polymer, creating an end-capped or terminally capped resinpolymer.

The term “pendant” is used herein to indicate that the silane moleculeof Formula I can be grafted or attached to, or co-polymerized into anon-terminal position of a polymer, i.e., a position on the backbone ofthe polymer, not an end-point, to create a multi-derivatized polymerresin. Silane-functionalized moieties of Formula I are attached topendant positions of a polymer when the polymer chain unit to which thesilane-functionalized moiety is attached occupies an internal positionfrom either end of the polymer backbone, whereas end-capped or end-pointsilane moieties are attached to the ultimate chain unit at either end ofthe polymer (resin). Polymer types suitable for silane functionalizationaccording to the described methods include, but are not limited to, puremonomer thermoplastic resin (PMR), C5 thermoplastic resin, C5/C9thermoplastic resin, C9 thermoplastic resin, terpene thermoplasticresin, indene-coumarone (IC) thermoplastic resin, dicyclopentadiene(DCPD) thermoplastic resin, hydrogenated or partially hydrogenated puremonomer (PMR) thermoplastic resin, hydrogenated or partiallyhydrogenated C5 thermoplastic resin, hydrogenated or partiallyhydrogenated C5/C9 thermoplastic resin, hydrogenated or partiallyhydrogenated C9 thermoplastic resin, hydrogenated or partiallyhydrogenated dicyclopentadiene (DCPD) thermoplastic resin, terpenethermoplastic resin, modified indene-coumarone (IC) thermoplastic resin.

Silane Functionalization of Resins

Disclosed are resins that are functionalized to include silane moleculescomprising various appendages. The functionalized resins disclosedherein possess different structures and can be manufactured orsynthesized using numerous methodologies, approaches, and strategies.For instance, several possible synthetic routes to the functionalizedresins disclosed herein are schematically shown in FIGS. 1A through 1M.That is, FIG. 1A through FIG. 1M provide schematic descriptions ofseveral exemplary embodiments of synthesis strategies to derive thesilane-containing resins disclosed herein.

As a non-limiting example thereof, phenol-containing resins with eitherin-chain pendant functionality from co-polymerization withacetoxystyrene or functional monomers can be used to provide thestarting material for silane functionalization. Resins employed asstarting material can include any one or more of known styrene-basedresins or poly(alpha-methyl)styrene (AMS) resins, for example. Otherresins that are employed as starting materials and that arefunctionalized according to the disclosed embodiments herein include anyknown to one of skill, including fully hydrogenated resins, partiallyhydrogenated resins, and resins that are not hydrogenated. For example,suitable resins known in the art and useful as starting material for thedisclosed processes for manufacturing silane-functionalized resinsinclude, but are not limited to, pure monomer thermoplastic resin (PMR),C5 thermoplastic resin, C5/C9 thermoplastic resin, C9 thermoplasticresin, hydrogenated or partially hydrogenated pure monomer (PMR)thermoplastic resin, hydrogenated or partially hydrogenated C5thermoplastic resin, hydrogenated or partially hydrogenated C5/C9thermoplastic resin, hydrogenated or partially hydrogenated C9thermoplastic resin, hydrogenated or partially hydrogenateddicyclopentadiene (DCPD) thermoplastic resin, terpene thermoplasticresin, and indene-coumarone (IC) thermoplastic resin.

As a further non-limiting example of the general synthetic strategiesthat can be employed to obtain the disclosed silane-functionalizedresins, end-capped resins with phenol end groups can be used in thesesame synthetic reactions, leading to resins having one or multipleterminal functionalization groups. As another exemplary embodiment,phenol groups can be reacted in a Williamson ether synthetic routefollowed by a mixed anhydride reaction to yield silane-containing resinsas in FIG. 1C. Reaction of phenol-based resins with ananhydride-containing silane was also successful. Other syntheticstrategies yield pendant functionalized resins that can yield thedesired degree of functionalization at internal positions.

Functionalized resins can be in the form of block copolymer andalternatively, silane moieties of the functionalized resin can occurrandomly throughout the polymer, distributed more or less evenlythroughout the resin backbone. That is, non-limiting examples offunctionalized resins disclosed herein includes resins formed by a blockcopolymer method, as well as functionalization of already formed resins,thereby creating a resin that has random monomers functionalizedthroughout the resin backbone. Further, functionalized resins disclosedherein can be synthesized starting from resin monomers, where the resinmonomers are reacted with silane moieties directly to formfunctionalized resin in one step, as depicted in Scheme 5.Functionalized resins can also be synthesized by starting with fullyformed resins, such as those disclosed in Schemes 1-4, Examples 1 and 2,below.

The silane-functionalized resins disclosed herein possess the followinggeneral chemical structure of Formula I, where “resin” represents thebackbone of the resin, as shown for example in FIGS. 1A to 1E and FIG.1G to 1M:

resin-[Z_(k)—X_(n)—R¹—(CH₂)_(m)—Si(R²)_(p)]_(q)  (I)

-   -   wherein Z is an aromatic group or an aliphatic group optionally        containing a heteroatom;    -   wherein X is a linker comprising a heteroatom selected from        sulfur, oxygen, nitrogen, a carbonyl group, or a combination        thereof;    -   wherein R¹ comprises one or more of an aliphatic and/or aromatic        C₁ to C₁₈ and/or a linkage group comprising a heteroatom;    -   wherein each R² is the same or different and is independently        selected from a C₁ to C₁₈ alkoxy, aryloxy, alkyl, aryl, or H, or        OH, and is optionally branched, and wherein at least one R² is        C₁ to C₁₈ alkoxy, aryloxy, or H, or OH;    -   wherein q is an integer from of at least 1;    -   wherein k is an integer of 0 or 1;    -   wherein n is an integer from 1 to 10;    -   wherein m is an integer from 0 to 10; and,    -   wherein p is 1, 2, or 3.

Typically, the carbon chain linker between heteroatom group R¹ and thesilane group Si(R²)_(p) is a methylene group, but a shorter or longercarbon chain linker can also be used. Urethane linkages are formed byreaction of phenol or hydroxyl group containing resins with silane basedisocyanates (triethoxysilylpropyl isocyanate) producing a functionalizedresin with the Formula: resin-OCONH—(CH₂)₃—Si(OCH₂CH₃)₃. Reacting phenolor hydroxyl based resins with anhydride silanes, for example,3-(triethoxysilyl)propyl succinic anhydride, results in the formation ofester linkages to form a functionalized resin having the formula:resin-O—CO—CH(CH₂COOH)((CH₂)₃—Si(OCH₂CH₃)₃). Ester linkages to the resinmay also be obtained through esterification or transesterification.Ether linkages with oxygen to the backbone can be derived via aWilliamson ether synthesis of resin-OH directly with alkylhalidefunctionalized silanes, for example, Cl—(CH₂)₃Si(OCH₂CH₃)₃, to formresin-O—(CH₂)₃—Si(OCH₂CH₃)₃. With other reagents, such as sodiumchloroacetate, post-modification after the Williamson ether synthesis isrequired to obtain silane functionalized resins, for example byresin-O—CH₂COOH reaction with ethyl chloroformate and3-(aminopropyl)triethoxysilane to formresin-O—CH₂CO—NH—(CH₂)₃—Si(OCH₂CH₃)₃. Any rosin acid-resin copolymers orany resin-COOH can be functionalized with ethyl chloroformate and3-(aminopropyl)triethoxysilane to form resin-CO—NH—(CH₂)₃—Si(OCH₂CH₃)₃.For example, resin-COOH can be obtained by grafting of succinicanhydride onto styrene or alpha-methyl styrene using a Lewis acidcatalyst to form resin-CO—(CH₂)₂—COOH. Further functionalization yieldsresin-CO—(CH₂)₂—CO—NH—(CH₂)₃—Si(OCH₂CH₃)₃. Maleic anhydride can begrafted onto resins containing unsaturation to obtainresin-CO—NH—(CH₂)₃—Si(OCH₂CH₃)₃ through ring-opening of the anhydridewith triethoxysilylpropyl amine.

The copolymers could include any number of other comonomers but mostlikely include either a resin of styrene or alpha-methyl styrene, ormixtures thereof. This is a preferred embodiment that the resin includesstyrene and/or alpha-methyl styrene, or mixtures thereof. The phenolattachment to the resin can be at any location on the ring, such as andincluding, para, ortho, and meta.

In a typical embodiment, Z is an aromatic group, more typically a6-membered aromatic group. In another typical embodiment, Z is asaturated or unsaturated cyclo-aliphatic group. Further, the variable Zcan contain one or more heteroatoms as disclosed in the scheme presentedin FIG. 1F. The heteroatom can be one or more of oxygen, sulfur, and/ornitrogen.

In yet another typical embodiment, X is oxygen or a carbonyl. In afurther embodiment, X can be sulfur. In a particular embodiment, thevinylaromatic monomer can be a styrene or alpha-methylstyrene, ormixtures thereof. In another particular embodiment, theheteroatom-containing linkage group X is comprises a para-, meta-, orortho-attached phenol, a hydroxyl, an amine, an imidazole, an amide, acarboxylic acid, an isocyanate, a urethane, a urea, a ketone, ananhydride, an ester, an ether, a thioether, a sulfoxide, a sulfone, asulfonamide, a sulfonium, an ammonium, a maleimide, or pyridiniumlinkers to covalently attach a silane group, and/or a carbonate ester.In yet another particular embodiment, X_(n)R¹—(CH₂)_(m) comprises one ormore groups containing a urethane, an ester, an ether, a ketone, anamide, and a propyl.

Typically, each R² is the same or different and is independentlyselected from a C₁ to C₁₈ alkoxy, aryloxy, alkyl, aryl, or H, or OH, andis optionally branched, and wherein at least one R² is C₁ to C₁₈ alkoxy,aryloxy, or H, or OH.

Silane-containing groups grafted onto the resins disclosed herein can belocated at the ends of the polymer resin units, i.e. end-capped, orrandomly distributed along the polymer backbone, i.e. at a pendantposition within the polymer resin, or any combination thereof, i.e. bothend-capped and pendant. In an end-capped functionalized resinembodiment, the amount of silane-containing groups grafted onto thefunctionalized resin is from 0.001 to 100 mol %, more commonly 0.1 to 50mol %, and most commonly 0.1 to 30 mol %, from 0.1 to 25 mol %, 0.1 to20 mol %, 0.1 to 15 mol %, 0.1 to 10 mol %, or 0.1 to 9 mol %. In oneembodiment, the amount of silane-containing groups grafted onto theresin is of from 0.01 to 30 mol %.

In another embodiment, the silane-containing group of Formula I islocated at one or more pendant positions within the polymer. In suchembodiments, an amount of silane-containing groups grafted onto theresins is about 0.0001 to about 100 mol %, about 0.1 to about 30 mol %,about 0.1 to about 50 mol %, or about 0.1 to about 100 mol %.

In another non-limiting embodiment, more than one silane functionalgroup, i.e., —R¹—(CH₂)_(m)—Si(R²)_(p), is attached to the same linkergroup X, or R¹. The silane groups on the same linker group can be thesame or different. Further, the functionalized resins disclosed hereinencompass R¹ and X moieties that contain branch points that can alsocontain one or more silane functionalizations (see, for example, Scheme3 of Example 1.3, below).

With particularity, the resin can have a molecular weight (Mw) of from200 to 200,000 g/mol, more commonly 200 to 175,000 g/mol, more commonly200 to 150,000 g/mol, from 200 to 125,000 g/mol, from 200 to 100,000g/mol, from 200 to 75,000 g/mol, and most commonly from 200 to 50,000g/mol. In another typical embodiment, the resin has a molecular weightof from 400 g/mol to 200,000 g/mol, more commonly 400 to 175,000 g/mol,more commonly 400 to 150,000 g/mol, from 400 to 125,000 g/mol, from 400to 100,000 g/mol, from 400 to 75,000 g/mol, and most commonly 400 to50,000 g/mol. In yet another typical embodiment, the resin has amolecular weight of from 400 to 25,000 g/mol.

In another embodiment, the resin can have any polydispersity index (PDI)of from 1 to 10, 1 to 9, 1 to 8, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3,or 1 to 2. In another typical embodiment, the resin can have anymolecular weight or PDI but must have a Tg low enough to compound withrubber formulations at 150 to 160° C. and must compound with variousrubbers or mixtures of rubbers and other additives at this temperature.

In an embodiment, the resin has a glass transition temperature Tg below200° C. In another embodiment, the Tg is under 190° C., 180° C., 170°C., 160° C., 150° C., 140° C., 130° C., 120° C., 110° C., 100° C., 90°C., 80° C., 70° C., 60° C., 50° C., 40° C., 30° C., 20° C., 10° C., 0°C., −5° C., −10° C., −15° C., −20° C., −25° C., or −30° C. Moreparticularly, in one embodiment, the Tg is no less than −10° C. Inanother embodiment, the Tg is not higher than 70° C.

In another embodiment, the resin comprises one or more terminalfunctional groups —[Z_(k)—X_(n)—R¹—(CH₂)_(m)—Si(R²)_(p)]_(q). Moreover,the resin is typically functionalized with one or multiple (q) moietiesZ_(k)—X_(n)—R¹—(CH₂)_(m)—Si(R²)_(p) bound pendant to a backbone of theresin in a random, segmented, or block structure. In another embodiment,the side chains are end-capped. In yet another embodiment, the sidechains are a mixture of end-capped and pendant.

With particularity, the functionalized resin is bound to a silicaparticle via a Si—O—Si link following hydrolysis of at least one —R²group. Also with particularity, a functionalized resin molecule islinked to a second functionalized resin molecule via a Si—O—Si linkfollowing hydrolysis of at least one —R² group. Further, bridged sidechains can be formed in which the Si group is covalently bound to itselfthrough the one, two, or three R² groups.

In a typical embodiment, R¹ is —O—CO—NH—R³—(CH₂)₂—, O—CO—R³—(CH₂)₂—,—O—CH₂—R³—(CH₂)₂—, —CO—R³—(CH₂)₂—, —CO—NH—R³—(CH₂)₂—, or a mixturethereof, and R³ is an aliphatic or aromatic C₁ to C₈ carbon chain,optionally branched, and/or optionally comprising one or moreheteroatoms. Preferably, R³ is an aliphatic or aromatic C₁ to C₈ carbonchain.

In general Formula I, n can be an integer from 1 to 10, 1 to 9, 1 to 7,1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 to 2. Furthermore, the variable mcan be any integer from 0 to 10, 1 to 10, 2 to 10, 3 to 10, 4 to 10, 5to 10, 6 to 10, 7 to 10, 8 to 10, or 9 to 10. The variables n and m canseparate by any range of integers between these as well, such as 1 to 2,2 to 3, 3 to 4, 4 to 5, 5 to 6, 6 to 7, 7 to 8, 8 to 9, or 9 to 10, orany other range therein. Particularly, m can be from 0 to 3, from 1 to3, or from 2 to 3.

Formula I encompasses several preferred embodiments. As an example, afew non-limiting embodiments of the functionalized resin comprise thefollowing structures:

resin-[Z_(k)—CH₂—Si(R²)_(p)]_(q)

resin-[Z_(k)—O—CO—R—(CH₂)₂—CH₂—Si(R²)_(p)]_(q)

resin-[Z_(k)—O—CH₂—R—(CH₂)₂—CH₂—Si(R²)_(p)]_(q)

resin-[Z_(k)—CO—(CH₂)₂—CH₂—Si(R²)_(p)]_(q),

resin-[Z_(k)—CO—NH—R—(CH₂)₂—CH₂—Si(R²)_(p)]_(q),

where Z is an aromatic or aliphatic containing group and the number ofsilane attachments, and “q” can be any integer of at least 1, buttypically is 1 to 20, 1 to 19, 1 to 18, 1 to 17, 1 to 16, 1 to 15, 1 to14, 1 to 13, 1 to 12, 1 to 11, 1 to 10, 1 to 9, 1 to 8, 1 to 7, 1 to 6,1 to 5, 1 to 4, 1 to 3, or 1 to 2, and where the silane functionalgroups are attached at the end or pendant to the resin chain, or amixture thereof. In these embodiments, k can be an integer of 0 or 1.

Other non-limiting embodiments of functionalized resins can include, forinstance, the following structures:

resin-[Z_(k)—O—CH₂CO—NH—(CH₂)₃—Si(OCH₂CH₃)₃]_(q),

resin-[Z_(k)—O—CO—CH(CH₂COOH)—(CH₂)₃—Si(OCH₂CH₃)₃]_(q),

resin-[Z_(k)—CO—NH—(CH₂)₃—Si(OCH₂CH₃)₃]_(q),

resin-[Z_(k)—CO—(CH₂)₂—CO—NH—(CH₂)₃—Si(OCH₂CH₃)₃]_(q),

resin-[Z_(k)—O—CO—NH—(CH₂)₃—Si(OCH₂CH₃)₃]_(q),

resin-[Z_(k)—O—(CH₂)₃—Si(OCH₂CH₃)₃]_(q).

where Z is a group comprising an aliphatic or aromatic group, forexample a styrene or a benzene ring structure or alternativelycontaining a long C₁ to C₁₈ aliphatic chain, and where the number ofsilane attachments “q” can be any number but typically 1 to 20, 1 to 19,1 to 18, 1 to 17, 1 to 16, 1 to 15, to 14, 1 to 13, 1 to 12, 1 to 11, 1to 10, 1 to 9, 1 to 8, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, or 1 to2, attached at the end, or pendant to the resin chain, or a mixturethereof. In these embodiments, k can be an integer of 0 or 1.

Additional preferred, non-limiting, exemplary embodiments of thedisclosed silane functionalized resins possess the following generalstructure: resin-[Z_(k)—X_(n)—R¹—(CH₂)_(m)—Si(R²)_(p)]_(q):

resin-Z_(k)—SO₂NH—(CH₂)₂—CH₂—Si(OCH₂CH₃)₃,

resin-Z_(k)—SONH—(CH₂)₂—CH₂—Si(OCH₂CH₃)₃,

resin-Z_(k)—S—(CH₂)₂—CH₂—Si(OCH₂CH₃)₃,

resin-Z_(k)—SO—(CH₂)₂—CH₂—Si(OCH₂CH₃)₃,

resin-Z_(k)—SO₂—(CH₂)₂—CH₂—Si(OCH₂CH₃)₃,

resin-(Z_(k)(COO—R—(CH₂)₂—Si(OCH₂CH₃)₃))_(q)-resin,

resin-[Z_(k)(COO(CH₂)₂OCOC(COCH₃)N(CH₂)₃Si(OCH₃)₃)]_(q)-resin,

resin-Z_(k)—SO₂NH—(CH₂)₂—CH₂—Si(OCH₂CH₃)₃,

resin-Z_(k)-Ph-O—Si(OCH₂CH₃)₃.

Further exemplary silane structures can be obtained, and thereby providefurther silane-functionalized resins, resulting from sol-gel chemistrywith hydrolysis or substitution of Si(R²)_(p) with Si(OH)_(n), where nis an integer from 1 to 3 for one or more of the silane R² groups. Afterhydrolysis, condensation of any two Si(OH)_(n) groups can occur to formSi—O—Si structures linking resin-to-resin, resin-to-other commercialsilanes, resin to functionalized rubber grades, or resin-to-filler. TheR² group on —Si(R²)_(p) can be selected, for example, as a heteroatomcontaining or carbon chain linker to another similar resin, a linker toanother type of silane-functionalized resin, a linker to an additionalsmall molecule silane or a silane polysulfide can be used, for example,bis[3-(triethoxysilyl)propyl]tetrasulfide (for instance, Si69®, EvonikIndustries AG, Essen, Germany) or bis[3-(triethoxysilyl)propyl]disulfide (for instance, Si266®, Evonik Industries AG, Essen, Germany),a linkage to a filler particle, or a linkage to a functionalized rubbergrade. These non-limiting exemplary structures include Si—O—Si bonds.Any known combination of condensed resin to resin is possible, i.e.inter-chain bond formation between two different silane-containinggroups, and/or intra-chain bond formation within the samesilane-containing group, resin to other silane, resin to functionalizedrubber grade, or resin to filler structures are possible whereby Si(OH)condenses to Si—O—Si to connect two Si-containing groups. In anotherembodiment, the functionalized resins can include an aromatic group (Ar)as the Z-group, for example, resulting in the structuresresin-Ar—O—R¹—(CH₂)_(m)—Si(R²)_(p) orresin-Ar—CO—R¹—(CH₂)_(m)—Si(R²)_(p).

In another non-limiting embodiment, X is an oxygen atom and the phenolgroup comes from the resin synthesis with phenol as a chain terminatingreagent, or use of acetoxystyrene co-monomer to derivehydroxystyrene-containing resins. The carbonyl (C═O) group attachmentcan come from, for example, a group grafted onto a styrene oralpha-methyl styrene using succinic anhydride, or another anhydride anda Lewis acid catalyst, such as aluminum chloride. Exemplary embodimentsin which X is a carbonyl (C═O) can be obtained from several possiblemethods, for instance grafting maleic anhydride onto the backbone of anunsaturated C5 or C5 copolymerized resin.

Compositions Comprising Silane-Functionalized Resins

The functionalized resins described above can be incorporated intovarious chemical compositions with numerous applications. The chemicalcompositions are, for example, solvent borne, waterborne, emulsions,100% solids, or hot melt compositions/adhesives. For instance, thealkoxy silane low molecular weight polymers (Mw<30000) can be blendedwith other polymers. More specifically, in one embodiment, variousthermoplastic polymers and elastomers, such as ethylene-vinyl acetate(EVA) or poly(ethylene-vinyl) acetate (PEVA) compounds, variouspolyolefins and alpha-polyolefins, reactor-ready polyolefins,thermoplastic polyolefins, elastomers (such as styrene-butadiene rubber(SBR), butadiene rubber (BR), and natural rubber), polyesters, styreneblock copolymers, acrylics, and acrylates can be blended with thedisclosed functionalized resins. Provided below are several non-limitingexamples of how the disclosed functionalized resins can be incorporatedinto various products to impart on these products beneficial and usefulproperties not previously available.

In one embodiment, the functionalized resin is blended with analkoxysilane low molecular weight polymer that can be used as anadditive to be utilized in the same way a typical low molecular weightpolymer would be used. The presence of the functionalized resinsdisclosed herein in a composition with an alkoxysilane low molecularweight polymer enhances processability (higher melt flow rate, lowerviscosity), and promotes adhesion. The alkoxysilane low molecular weightpolymer further reacts after processing, thereby resulting in across-linked polymer that increases performance of a final articleincorporating such a blended resin with regards to temperatureresistance and chemical resistance. If the polymer being modified hasalkoxysilane functionality, the low molecular weight polymer can graftto the polymer being modified in addition to cross-linking with itself.Additionally, the ability to further react is beneficial in filledsystems (particles, fibers, etc.) where the alkoxysilane chemicallybonds to surface groups on the various fillers.

In another embodiment, a styrene-ethylene/butylene-styrene blockcopolymer (e.g., Kraton® G1650, Kraton Polymers U.S., LLC, Houston,Tex., US) is blended/processed with about 20% by weight of analkoxysilane functionalized polystyrene at a temperature belowactivation of the hydrolysis and crosslinking of the alkoxysilane. Theblend can optionally include other additives, such as, for instance,thermoplastic polymers, oils, and fillers. After processing into anarticle (film, fiber, profile, gasket, PSA tapes, molded handles,sealants, etc.), the article is exposed to temperatures sufficient toinduce hydrolysis and subsequent reaction of the alkoxysilane. Forthermoplastic elastomer applications like film, fiber profiles, andgaskets, there is an improvement in high temperature compression set andchemical resistance. For tape applications, the chemical crosslinkingcan be triggered in the same way with an increase in shear resistance,shear adhesive failure temperature, and chemical resistance.

In another embodiment, disclosed are disposable hygiene articlescomprising an adhesive comprising the disclosed silane-functionalizedresins that exhibit improved adhesive strength and cohesive strength byimproved values in peel adhesion testing of the laminate construction,improved peel adhesion after aging at body temperature, reduced creep ofelastic strands over time, and improved core stability in a finalhygiene article, as compared to such articles without the disclosedsilane-functionalized resins. Said articles possess improved chemicalresistance and barrier properties, particularly regarding exposure tofluids such as body fluids.

The polymer compositions further optionally include polyolefinscomprising amorphous or crystalline homopolymers or copolymers of two ormore different monomers derived from alpha-mono-olefins having from 2 toabout 12 carbon atoms, or from 2 to about 8 carbon atoms. Non-limitingexamples of suitable olefins include ethylene, propylene, 1-butene,1-pentene, 1-hexene, 2-methyl-i-propene, 3-methyl-i-pentene,4-methyl-i-pentene, 5-methyl-i-hexene, and combinations thereof.Additional suitable polyolefins include, but are not limited to, lowdensity polyethylene, high-density polyethylene, linear-low-densitypolyethylene, poly-propylene (isotactic and syndiotactic),ethylene/propylene copolymers, polybutene, and olefinic blockcopolymers. Polyolefin copolymers also include the greater part byweight of one or more olefin monomers and a lesser amount of one or morenon-olefin monomers, such as vinyl monomers including vinyl acetate, ora diene monomer, EPDM, and the like. Generally, a polyolefin copolymerincludes less than about 30 weight percent of a non-olefin monomer, lessthan 20 weight percent, or less than about 10 weight percent of anon-olefin monomer. Polyolefin polymers and copolymers are commerciallyavailable from sources including, but not limited to, Chevron, DowChemical, DuPont, Exxon Mobil, REXtac, LLC, Ticona, and Westlake Polymerunder various designations.

Migration and volatilization of low molecular weight components ofcurrently commercially available thermoplastic resins used to modifyelastomeric compounds such as adhesives, thermoplastic elastomer (TPE)compounds, molding compounds, mastics, etc. causes release of unpleasantodors, volatiles, fogging, product defects, reduced product cohesivestrength, reduced adhesion, and degradation of performance over time.

TPE compositions incorporating the silane-functionalized, or modified,resins described herein are in some embodiments formed into a variety ofarticles as well understood by those of ordinary skill in the art. Forexample, TPE compositions are reprocessed, such as by being pressed,compression molded, injection molded, calendared, thermoformed,blow-molded, or extruded into final articles and embodiments thereof.When reprocessing TPE compositions, the composition is generally heatedto a temperature of at least the softening or melting point of thethermoplastic component of the TPE composition in order to facilitatefurther forming into desired articles of various shapes and sizes. Theend user of the TPE compositions will benefit by the processingadvantages described throughout this disclosure.

Any polymer known in the art can be mixed with the silane-functionalizedresins described herein to create compositions useful in various endproducts such as adhesives, described herein. For instance, in oneembodiment, TPEs include, but are not limited to, block copolymersthermoplastic/elastomer blends and alloys, such as styrenic blockcopolymers (TPE-S), metallocene-catalyzed polyolefin polymers andelastomers, and reactor-made thermoplastic polyolefin elastomers. Blockcopolymers include, but are not limited to, styrenic block copolymer,olefin block copolymer, co-polyester block copolymer, polyurethane blockcopolymer and polyamide block copolymer. Thermoplastic/elastomer blendsand alloys include, but are not limited to, thermoplastic polyolefinsand thermoplastic vulcanizates. Two-phase TPEs are in some embodimentscombined with the disclosed modified thermoplastic resins in these enduse applications described herein. TPE-S copolymers include, but are notlimited to, styrene-butadiene-styrene block copolymer (SBS),styrene-ethylene/butylene-styrene block copolymer (SEBS),styrene-ethylene-ethylene/propylene-styrene block copolymer (SEEPS), andstyrene-isoprene-styrene block copolymer (SIS).

That is, the disclosed modified silane resins are used in someembodiments to modify the properties of thermoplastic elastomer (TPE)compositions. Embodiments therefore include TPE compositions comprisingat least one thermoplastic elastomer and at least one modified silaneresin. Earlier versions of TPEs are thermoset rubbers that can also beutilized in such compositions. TPEs are known to be widely used invarious industries to modify the properties of rigid thermoplastics,imparting improvements in impact strength. This is quite common forsheet goods and general molding TPEs. Thus, addition of the modifiedsilane resins described herein to these compositions imparts furtherexcellent properties to these compositions and their standard end uses.

The TPE compositions comprising the disclosed silane-functionalizedresins incorporate any TPE known in the art. In one embodiment, TPEsinclude at least one or a combination of block copolymers,thermoplastic/elastomer blends and alloys thereof, metallocene-catalyzedpolyolefin polymers and elastomers, and reactor-made thermoplasticpolyolefin elastomers. Block copolymers include, but are not limited to,styrenic block copolymer, copolyester block copolymer, polyurethaneblock copolymer, and polyamide block copolymer. Thermoplastic/elastomerblends and alloys useful in such compositions include, but are notlimited to, thermoplastic polyolefins and thermoplastic vulcanizates.

Various known TPE types, such as block copolymers andthermoplastic/elastomer blends and alloys, are known as two-phasesystems. In such systems, a hard thermoplastic phase is coupledmechanically or chemically with a soft elastomer phase, resulting in aTPE that has the combined properties of the two phases.

Styrenic block copolymers (TPE-S) are based on a two-phase blockcopolymer with hard and soft segments. Exemplary styrenic blockcopolymers include, but are not limited to, styrene-butadiene-styreneblock copolymer (SBS), styrene-ethylene/butylene-styrene block copolymer(SEBS), styrene-ethylene-ethylene/propylene-styrene block copolymer(SEEPS), styrene-isoprene-styrene block copolymer (SIS).Styrene-butadiene-styrene is known to be commonly incorporated intocompositions for use in footwear, adhesives, bitumen modification, andlower specification seals and grips, where resistance to chemicals andaging is not a focus of the end use. Monoprene®, Tekron®, and Elexar®products from Teknor Apex Company (Pawtucket, R.I., US) are examples offully formulated TPE-S compounds that are hydrogenated styrenic blockcopolymers. Styrene-[ethyl ene-(ethylene/propylene)]-styrene (SEEPS)block copolymer is available from Kuraray Co., Ltd, Tokyo, Japan.Styrene-ethylene/butylene-styrene (SEBS) block copolymer is commerciallyavailable from Kraton Performance Polymers.

Table 1 presents expected performance enhancements from incorporation ofsilane functionalized resins in various applications where suchattributes are likely to be advantageous. Upper case “X” in Table 1indicates an attribute that is likely achievable by incorporation of thesilane functionalized resins disclosed herein into indicatedcompositions and that are desirable in each application.

TABLE 1 Attributes Adhesive Cohesive Enhanced Compatibility withstrength strength processability Heat resistance filled systems Chemicalresistance Barrier properties Applications TPE X X X X X X X compoundsPressure X X X X X X sensitive adhesives Disposable X X X X X (Hygieneparticularly elastic adhesives) Packaging X X X X X adhesives LaminatingX X X X X X adhesives Heat seal X X X X X X coatings/ adhesivesSealants/ X X X X X X X gaskets Investment X X X casting wax StructuralX X X X X X X adhesives Cementitious X X X X X X X adhesives Textilesizing X X X X X (woven, nonwoven) Attributes Noise and Dimensionaldifferent Different radiation Fire resistant vibration damping stabilityelectrical properties absorptive properties Applications TPE X X X X Xcompounds Pressure X X X X sensitive adhesives Disposable (Hygieneparticularly elastic adhesives) Packaging adhesives Laminating X Xadhesives Heat seal coatings/ adhesives Sealants/ X X X X X gasketsInvestment X casting wax Structural X X X X X adhesives Cementitious X XX adhesives Textile sizing X (woven, nonwoven)

Polymer modification applications for thermoplastic elastomers using thedescribed silane-functionalized resins include, but are not limited to,roofing applications (especially asphalt modifiers in modified bitumenroofing), water proofing membranes/compounds, underlayments, cableflooding/filling compounds, caulks and sealants, polymercompounds/blends, films, e.g., cling films, TPE films, and the like,molded articles, rubber additive/processing aids, carpet backing, e.g.,high performance precoat, thermoplastic compound, and the like, wire andcables, power and hand tools, pen grips, airbag covers, grips andhandles, seals, and laminated articles, e.g., paper lamination, wateractivated, hot melt gummed, scrim reinforced tape, and the like. Whenthe silane-functionalized resins described herein are incorporated intosuch end-use applications, the silane-functionalized resin is in someinstances the sole resin in the composition. In other embodiments, thesilane-functionalized resin is combined with other resins,elastomers/polymers, and/or additives. In such end-use embodiments, theaforementioned compositions comprise at least 1, 2, 3, 4, 5, 10, 15, 20,25, 30, 35, 40, 45, 50, 55, or 60 and/or not more than 99, 95, 90, 85,80, 75, 70, or 65 weight percent of at least one silane-functionalizedresin.

Thus, other embodiments include adhesives used in packaging, productassembly, woodworking, automotive assembly, and other applications thatare composed of ethylene vinyl acetate, ethyl ene-butyl-acrylate,semi-crystalline single-site catalyzed (metallocene) polyolefins,amorphous poly alpha-olefins such as Ziegler-Natta catalyzed polymers,acrylics, and styrene block copolymers. These products can exhibitimproved adhesive and cohesive strength as measured by peel adhesionfailure temperature (PAFT) testing, fiber tear testing, peel testing onadhered structures, shear adhesion failure temperature (SAFT) testing,IoPP (Institute of Packaging Professionals) test T-3006 Heat StressResistance of Hot Melt Adhesives, and shear hold power. Said adhesiveembodiments comprising the disclosed functionalized resins can exhibitimproved heat resistance as evidenced by fiber tear or peel adhesiontesting at elevated temperatures such as 60° C. Improved chemicalresistance may be shown by reduced degradation of adhesive and cohesivestrength after exposure to selected chemicals.

Compositions comprising the disclosed functionalized resins can act asbarriers to plasticizer migration, as evidenced to adhesioncharacteristics over time, as compared to compositions not including thedisclosed functionalized resins, particularly after heat aging, asevidenced by any of the test methods above: PAFT, SAFT, peel, fibertear, and shear hold power at and above room temperature. Similarly,said compositions adhere well to difficult surfaces or to substrateswith migratory components (e.g. slip aids or plasticizers), as evidencedby the above listed adhesion tests, as compared with adhesives that donot contain the disclosed functionalized resins.

Investment casting wax compositions comprising the disclosedfunctionalized resins possess excellent rheology for consistentproduction of parts, as evidenced by the composition rheology(stress-strain curves). Outstanding performance in dimensional stabilityof the wax casting composition and casting composition stability duringmold making are evidenced by improved tolerances on the cast product.

In another embodiment, compositions comprising the functionalized resinsinclude heat seal coatings and adhesives that exhibit excellent heatresistance according to peel adhesion testing at temperatures near andabove the sealing temperatures using ASTM F88.

In a further embodiment, disclosed are sealant compositions comprisingthe disclosed functionalized resins that exhibit reduced fogging ofsealed windows after aging as compared with the performance of sealantsnot comprising the disclosed functionalized resins.

The excellent structural stability of sealants and gaskets and otherrubber-based materials comprising the disclosed functionalized resins isevidenced by dimensional stability measurements following compression orelongation, as compared with sealants and gaskets and other rubber-basedmaterials not comprising the disclosed functionalized resins.

Vibration and sound damping improvement can be measured by ASTM E756 forsealants, gaskets, structural adhesives, cementitious, bitumen andasphalt adhesives, thermoplastic elastomer (TPE) compounds and pressuresensitive adhesives.

Also provided are compositions such as mastics containing bitumen,asphalt, or similar materials, that contain the disclosed functionalizedresins. Such compositions have lower viscosity than compositions notcomprising the disclosed functionalized resins, thereby allowing easierprocessing, while exhibiting excellent adhesion to aggregate components,fillers, and substrates, such as stone or cement, as evidenced bytensile testing on adhered stone or cement samples. Such mastics findapplication in the production of bridge decking, flooring, roadconstruction, and roofing.

In another embodiment, pressure sensitive adhesives (PSAs, tape, label,graphics protective films, window film) are provided that comprise thedisclosed functionalized resins.

One problem associated with pressure-sensitive adhesives (PSAs) based ontackified elastomeric blends is diffusion and migration of tackifiersand other species from the adhesive composition or article componentsinto the facestock or substrate. As a result, the facestock or substratemay become stained over time and the construction may lose someadhesion. This migration or bleed through of some or all components ofan adhesive, compounded film, or other composition comprisingthermoplastic resins can also leave a residue on the bonded surface uponremoval, such as with protective films, or can cause undesired surfacecontamination, skin irritation, etc. More critical to adhesiveapplications, compounds comprising thermoplastic resins or multilayerfilms, the migration or “bleed through” of chemical components towardsthe bonded interfaces, e.g. adhesive-substrate orfilm-adhesive-nonwoven, can cause immediate or delayed reduction orelimination of bond strength, damage to the bonded or laminated article,and/or reduction of adhesion with aging.

The aforementioned compositions comprising the silane-functionalizedthermoplastic resins in some embodiments further comprise at least onepolymer and about 0 to about 75 wt % un-modified thermoplastictackifying resin. In another embodiment, the adhesive compositioncomprises at least one thermoplastic elastomer and at least onethermoplastic resin, in addition to the silane-functionalized resin. Thethermoplastic elastomer can, for instance be one or more of hydrogenatedand/or nonhydrogenated styrenic block copolymers including, but notlimited to, styrene-butadiene-styrene block copolymer (SBS),styrene-ethylene/butylene-styrene block copolymer (SEBS),styrene-[ethylene-(ethylene/propylene)]-styrene block copolymer (SEEPS),and/or styrene-isoprene-styrene block copolymer (SIS). In anotherembodiment, the adhesive compositions described herein exhibit aviscosity at 177° C. of about 50 to about 10,000 cP, and a softeningpoint of about 60 to about 180° C. and are suitable adhesives.

In the composition embodiments described herein, the adhesivecompositions can comprise at least 1, 2, 3, 4, 5, 10, 15, 20, 25, 30,35, 40, 45, 50, 55, or 60 and/or not more than 99, 95, 90, 85, 80, 75,70, or 65 weight percent of at least one modified thermoplastic resin.

In various embodiments, the compositions comprise 10, 20, 30, or 40and/or not more than 90, 80, 70, or 55 weight percent of at least onepolymer component. Exemplary polymer components of the disclosedcompositions include, but are not limited to, ethylene vinyl acetatecopolymer, ethylene n-butyl acrylate copolymer, ethylene methyl acrylatecopolymer, polyester, neoprene, acrylics, urethane, poly(acrylate),ethylene acrylic acid copolymer, polyether ether ketone, polyamide,styrenic block copolymers, random styrenic copolymers, hydrogenatedstyrenic block copolymers, styrene butadiene copolymers, natural rubber,polyisoprene, polyisobutylene, atactic polypropylene, polyethyleneincluding atactic polypropylene, ethylene-propylene polymers,propylene-hexene polymers, ethylene-butene polymers, ethylene octenepolymers, propylene-butene polymers, propylene-octene polymers,metallocene-catalyzed polypropylene polymers, metallocene-catalyzedpolyethylene polymers, ethylene-propylene-butylene terpolymers,copolymers produced from propylene, ethylene, and various C4-C10alpha-olefin monomers, polypropylene polymers, functional polymers suchas maleated polyolefins, butyl rubber, polyester copolymers, copolyesterpolymers, isoprene, the terpolymer formed from the monomers ethylene,propylene, and a bicyclic olefin (known as “EPDM”), isoprene-based blockcopolymers, butadiene-based block copolymers, acrylate copolymers suchas ethylene acrylic acid copolymer, butadiene acrylonitrile rubber,and/or polyvinyl acetate.

The compositions disclosed herein, in various embodiments, containpolymer, tackifier resin, and other additives such as, but not limitedto, oils, waxes, plasticizers, antioxidants, and fillers, depending onthe end use application. In various embodiments, the compositionscomprise at least about 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50, and/ornot more than 500, 450, 400, 350, or 300 parts of polymer, tackifierresin, and/or other additives per 100 parts of modified thermoplasticresin. For example, in one embodiment, the compositions disclosed hereincontain about 50 to about 300 parts of elastomer per 100 parts ofsilane-functionalized resin.

As noted above, in some embodiments, the described compositions compriseadditives particularly suitable for a specific end-use application. Forexample, if the adhesive is intended to serve as a hot melt packagingadhesive, as noted above, then in this embodiment, the composition willfurther comprise a wax. In some embodiments, the adhesive compositioncomprises at least 1, 2, 5, 8, or 10 and/or not more than 40, 30, 25, or20 weight percent of at least one wax. In another embodiment, thecompositions described herein comprise about 1 to about 40, about 5 toabout 30, about 8 to about 25, or about 10 to about 20 weight percent ofat least one wax. Suitable waxes include, without limitation,microcrystalline wax, paraffin wax, waxes produced by Fischer-Tropschprocesses, vegetable wax, functionalized waxes (maleated, fumerated, orwax with functional groups), and the like. In such embodiments, a wax isincluded in the composition in an amount of between about 10 and about100 parts wax per 100 parts of the polymer component.

In pressure sensitive adhesive (PSA) composition embodiments, such asadhesives used in tapes, mastics, and labels, and in nonwovenapplications of the described adhesive compositions, various oils areadded to the adhesive compositions. In one embodiment, the adhesivecomposition comprises at least about 1, 2, 5, 8, or about 10 and/or notmore than about 40, 30, 25, or about 20 weight percent of at least oneprocessing oil. In another embodiment of pressure sensitive adhesivecompositions, the adhesive compositions comprise about 2 to about 40,about 5 to about 30, about 8 to about 25, or about 10 to about 20 weightpercent of at least one processing oil. Processing oils include, but arenot limited to, mineral oils, naphthenic oils, paraffinic oils, aromaticoils, castor oils, rape seed oil, triglyceride oils, and combinationsthereof. Processing oils also include extender oils that are commonlyused in various pressure-sensitive adhesive compositions. In anotherembodiment, the described adhesive composition comprises no processingoils.

In another embodiment of the compositions, one or more plasticizers areadded to the adhesive compositions, such as, but not limited to,phthalate esters such as, for example, dibutyl phthalate and dioctylphthalate, benzoates, terephthalates, and chlorinated paraffins. In oneembodiment, the described adhesive compositions comprise at least about0.5, 1, 2, or about 3 and/or not more than about 20, 10, 8, or about 5weight percent of at least one plasticizer. In another embodiment, theadhesive compositions comprise about 0.5 to about 20, about 1 to about10, about 2 to about 8, or about 3 to about 5 weight percent of at leastone plasticizer. Other exemplary plasticizers include Benzoflex™ andEastman 168™ (Eastman Chemical Company, Kingsport, Tenn., US).

In other embodiments, the compositions that incorporate one or moresilane-functionalized resins further comprise at least about 0.1, 0.5,1, 2, or about 3 and/or not more than about 20, 10, 8, or about 5 weightpercent of at least one antioxidant. Any antioxidant known to a personof ordinary skill in the art may be used in the adhesion compositionsdisclosed herein. Non-limiting examples of suitable antioxidants includeamine-based antioxidants such as alkyl diphenyl amines,phenyl-naphthylamine, alkyl or aralkyl substituted phenyl-naphthylamine,alkylated p-phenylene diamines, tetramethyl-diaminodiphenylamine and thelike; and hindered phenol compounds such as2,6-di-t-butyl-4-methylphenol;1,3,5-trimethyl-2,4,6-tris(3′,5′-di-t-butyl-4′-hydroxybenzyl)benzene;tetra kis [(methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane,such as IRGANOX® 1010 (BASF Corp., LA, US);octadecyl-3,5-di-t-butyl-4-hydroxycinnamate, such as IRGANOX® 1076 (BASFCorp., LA, US) and combinations thereof. Where used, the amount of theantioxidant in the composition can be from about greater than 0 to about1 wt %, from about 0.05 to about 0.75 wt %, or from about 0.1 to about0.5 wt % of the total weight of the composition. In another suchembodiment, the adhesive compositions comprise about 0.1 to about 20,about 1 to about 10, about 2 to about 8, or about 3 to about 5 weightpercent of at least one antioxidant.

In another embodiment of the compositions, the composition comprises oneor more fillers, such as, but not limited to, carbon black, calciumcarbonate, clay and other silicates, titanium oxide, and zinc oxide. Inanother embodiment of the described compositions, the compositionscomprise at least about 10, 20, 30, or about 40 and/or not more thanabout 90, 80, 70, or about 55 weight percent of at least one filler. Ina further embodiment, the compositions comprise about 1 to about 90,about 20 to about 80, about 30 to about 70, or about 40 to about 55weight percent of at least one filler. In some embodiments, silica isadded as a filler, in addition to, or in lieu of, silicates foundpresent in clay and fly ash. That is, silica, i.e. a combination ofsilica and oxygen (SiO₂) is manufactured by known methods and arecommercially available in pure or relative pure form as a white powder.Silica, commonly formed by precipitate, are a synthetic crystallineamorphous form of silicon dioxide, derived from quartz sand. Such silicaand silicates are in some embodiments added to the compositions asfillers. Silica, apart from organosilanes used as coupling agents, iscommonly incorporated into rubber compositions that are used tomanufacture goods such as seals, cables, profiles, belts, and hoses.When used together, both synthetic (pure) silica as a filler, andorganosilanes present as coupling agents, a silica-silane system iscreated that is commonly employed or incorporated into industrial rubbergoods that require high reinforcement combined with the possibility tomanufacture white or colored products. In such contexts and embodiments,silica is incorporated as a filler to improve tear resistance, and insome embodiments, the silica-silane systems reduce heat buildup. (See,Uhrland, S., “Silica,” in Encyclopedia of Chemical Technology,Kirk-Othmer, John Wiley & Sons, Inc., 2006). In contrast, clays arecomposed of clay minerals of a fine particle size and are essentiallycombinations of silica, alumina, and water to create hydrated aluminumsilicates with associated alkali and alkaline earth elements. Such claysare a raw material found in clay deposits of varying composition andgrain size. Clays are used commonly as fillers in sealants andadhesives. For instance, sodium bentonites are incorporated intosealants as fillers that impart water impedance due to high swellingcapacity and to impede movement of water. Clays incorporated intoadhesives are in some instances in the form of attapulgite that improvesviscosity under shear. In other embodiments, incorporation of kaolinfiller can impact viscosity of the composition. Thus, clays have presentwithin them various hydrated aluminum silicates that are different anddistinguishable from silica that is synthetic, and in some embodimentsalso incorporated into the described compositions as a filler. (See,Id., Murray, H. H., “Clays, Uses” and “Clays, Survey”).

Additionally, other tackifier resins are present in various embodimentsof the described compositions, which are optionally present in the formof physical blends. Tackifier resins added to the described compositionsin this embodiment include, without limitation, cycloaliphatichydrocarbon resins, C5 hydrocarbon resins, C5/C9 hydrocarbon resins,aromatically modified C5 resins, C9 hydrocarbon resins, pure monomerresins, e.g., copolymers of styrene with alpha-methyl styrene, vinyltoluene, para-methyl styrene, indene, and methyl indene, DCPD resins,dicyclopentadiene based/containing resins, cyclo-pentadienebased/containing resins, terpene resins, terpene phenolic resins,terpene styrene resins, esters of rosin, esters of modified rosins,liquid resins of fully or partially hydrogenated rosins, fully orpartially hydrogenated rosin esters, fully or partially hydrogenatedmodified rosins resins, fully or partially rosin alcohols, fully orpartially hydrogenated C5 resins, fully or partially hydrogenated C5/C9resins, fully or partially hydrogenated DCPD resins, fully or partiallyhydrogenated dicyclopentadiene based/containing resins, fully orpartially hydrogenated cyclo-pentadiene based/containing resins, fullyor partially hydrogenated aromatically modified C5 resins, fully orpartially hydrogenated C9 resins, fully or partially hydrogenated puremonomer resins, e.g., copolymers or styrene with alpha-methyl styrene,vinyl toluene, para-methyl styrene, indene, and methyl indene, fully orpartially hydrogenated C5/cycloaliphatic resins, fully or partiallyhydrogenated C5/cycloaliphatic/styrene/C9 resins, fully or partiallyhydrogenated cycloaliphatic resins, and mixtures thereof.

In some embodiments, the compositions described herein include otherconventional plastic additives in an amount that is sufficient to obtaina desired processing or performance property for the adhesive. Theamount should not be wasteful of the additive nor detrimental to theprocessing or performance of the adhesive. Those skilled in the art ofthermoplastics compounding, without undue experimentation but withreference to such treatises as Plastics Additives Database (2004) fromPlastics Design Library (www.elsevier.com) can select from manydifferent types of additives for inclusion into the compounds describedherein. Non-limiting examples of optional additives include adhesionpromoters; biocides (antibacterials, fungicides, and mildewcides),anti-fogging agents; anti-static agents; bonding, blowing and foamingagents; dispersants; fillers and extenders; fire and flame retardantsand smoke suppressants; impact modifiers; initiators; lubricants; micas;pigments, colorants and dyes; oils and plasticizers; processing aids;release agents; silanes, titanates and zirconates; slip andanti-blocking agents; stabilizers (for example, Irganox® 1010 andIrganox® 1076, BASF Corporation, LA, US); stearates; ultraviolet lightabsorbers; viscosity regulators; waxes; and combinations thereof.Antioxidants are particularly useful for these compounds to provideadditional durability.

Such compositions are manufactured in one embodiment by blending thesilane-functionalized resin with an elastomer (at least one polymer) toform the adhesive. That is, the adhesive compositions described hereinare in one embodiment prepared by combining the silane-functionalizedresin, the elastomer, and the additives using conventional techniquesand equipment. As a non-limiting exemplary embodiment, the components ofthe compositions described herein are blended in a mixer such as a Sigmablade mixer, a plasticorder, a Brabender mixer, a twin-screw extruder,and/or an in-can blend can (pint-cans). In another embodiment, thecompositions are shaped into a desired form, such as a tape or sheet, byan appropriate technique including, for example, extrusion, compressionmolding, calendaring, or roll coating techniques (gravure, reverse roll,and the like). In some embodiments, the compositions described hereinare applied using curtain coating, slot-die coating, or sprayed throughdifferent nozzle configurations at different speeds using typicalapplication equipment.

In another embodiment, the compositions described herein are applied toa substrate by melting the composition and then using conventional hotmelt adhesive application equipment recognized in the art to coat thesubstrate with the composition. Substrates include, for example,textile, fabric, paper, glass, plastic, and metal materials. Typically,about 0.1 to about 100 g/m2 of adhesive composition is applied to asubstrate.

The silane-functionalized resins described herein, in some embodiments,are incorporated into various types of compositions including, but notlimited to, hot melt or solvent based pressure sensitive adhesives,e.g., tapes, labels, mastics, HVACs, and the like, hot melt nonwovenadhesives, e.g., those for use in the construction industry, for elasticattachment, or for stretching, and hot melt packaging adhesives.Furthermore, the silane-functionalized resins described herein inanother embodiment are incorporated into different polymer systems asexplained above to provide excellent physical and chemical properties interms of processability, stability, thermal properties, barrierproperties, viscoelasticity, vibration damping, rheology, volatility,fogging profiles, and/or adhesion and mechanical properties of suchpolymer systems. Moreover, the silane-functionalized resins describedherein enhance various physical and chemical properties in thermoplasticelastomer applications such as roofing applications (construction),adhesives, sealant applications, cable flooding/filling applications,and tire elastomer applications, e.g., tread compositions, side walls,inner liners, inner-tubes, and various other pneumatic tire components,for example.

While the preceding discussion is primarily directed to adhesiveapplications incorporating the silane-functionalized resins describedherein, these principals can be generally expanded and applied to otherpolymer compositions comprising the silane-functionalized resins for usein a myriad number of end products. For instance, polymer modificationapplications incorporating the silane-functionalized resins describedherein include, but are not limited to, roofing applications (such asasphalt modifiers in modified bitumen roofing), water proofingmembranes/compounds, underlayments, cable flooding/filling compounds,caulks and sealants, structural adhesives, polymer compounds/blends,films, e.g., cling films, TPE films, Biaxially Oriented PolyPropylene(BOPP) films, and the like, molded articles, rubber additive/processingaids, carpet backing, e.g., high performance precoat, thermoplasticcompound, and the like, wire and cables, power and hand tools, pengrips, airbag covers, grips and handles, seals, and laminated articles,e.g., paper lamination, water activated, hot melt gummed, scrimreinforced tape, and the like. When incorporated into these various enduse applications, the described silane-functionalized resins in someembodiments are the sole resin in the compositions. In otherembodiments, the silane-functionalized resins are combined with otherresins, elastomers/polymers, and/or additives. In such combined resinapplications, the aforementioned compositions comprise at least about 1,2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or about 60 and/ornot more than about 99, 95, 90, 85, 80, 75, 70, or about 65 weightpercent of at least one silane functionalized resin.

Thus, in various embodiments, one or more of the silane-functionalizedresins described herein are incorporated into hot melt adhesivecompositions. According to one or more embodiments, the adhesivestherefore comprise at least about 1, 5, 10, 20, 30, 40, 50, or 60 and/ornot more than about 95, 90, 80, 70, or 60 weight percent (wt %) of thesilane-functionalized resins, or mixtures thereof. Moreover, theadhesives in other embodiments comprise in the range of about 1 to 95, 5to 90, 10 to 80, 20 to 70, 30 to 60, or 40 to 60 weight percent of themodified thermoplastic resins described herein, or mixtures thereof. Incertain additional embodiments, the adhesives are entirely comprised ofone or more the silane-functionalized resins described herein.Furthermore, depending on the desired end use, these hot melt adhesivesalso comprise, in certain embodiments, various additives such as, forexample, polymers, tackifiers, processing oils, waxes, antioxidants,plasticizers, pigments, and/or fillers.

In various embodiments, the adhesives comprise at least about 5, 10, 20,30, or 40 and/or not more than about 95, 90, 80, 70, or 55 weightpercent of at least one thermoplastic tackifier resin that is differentfrom the silane functionalized resins described herein. Moreover, theadhesives comprise, in other embodiments, in the range of about 10 to90, 20 to 80, 30 to 70, or 40 to 55 weight percent of at least one resinthat is different from the silane-functionalized resins describedherein. Contemplated thermoplastic tackifier resins include pure monomerthermoplastic resin (PMR), C5 thermoplastic resin, C5/C9 thermoplasticresin, C9 thermoplastic resin, terpene thermoplastic resin,indene-coumarone (IC) thermoplastic resin, dicyclopentadiene (DCPD)thermoplastic resin, hydrogenated or partially hydrogenated pure monomer(PMR) thermoplastic resin, hydrogenated or partially hydrogenated C5thermoplastic resin, hydrogenated or partially hydrogenated C5/C9thermoplastic resin, hydrogenated or partially hydrogenated C9thermoplastic resin, hydrogenated or partially hydrogenateddicyclopentadiene (DCPD) thermoplastic resin, terpene thermoplasticresin, modified indene-coumarone (IC) thermoplastic resin, or a mixturethereof.

In various embodiments, the adhesives comprise at least about 10, 20,30, 40, 50, or 60 and/or not more than about 90, 80, 70, or 60 weightpercent of at least one tackifier. Moreover, the adhesives comprise insuch embodiments in the range of about 10 to 90, 20 to 80, 30 to 70, orabout 40 to 60 weight percent of at least one tackifier. Suitabletackifiers contemplated herein include, for example, cycloaliphatichydrocarbon resins, C5 hydrocarbon resins; C5/C9 hydrocarbon resins;aromatically-modified C5 resins; C9 hydrocarbon resins; pure monomerresins such as copolymers of styrene with alpha-methyl styrene, vinyltoluene, para-methyl styrene, indene, methyl indene, C5 resins, and C9resins; terpene resins; terpene phenolic resins; terpene styrene resins;rosin esters; modified rosin esters; liquid resins of fully or partiallyhydrogenated rosins; fully or partially hydrogenated rosin esters; fullyor partially hydrogenated modified rosin resins; fully or partiallyhydrogenated rosin alcohols; indene-coumarone (IC) thermoplastic resin,dicyclopentadiene (DCPD) thermoplastic resin, hydrogenated or partiallyhydrogenated dicyclopentadiene (DCPD) thermoplastic resin, fully orpartially hydrogenated C5 resins; fully or partially hydrogenated C5/C9resins; fully or partially hydrogenated aromatically-modified C5 resins;fully or partially hydrogenated C9 resins; fully or partiallyhydrogenated pure monomer resins; fully or partially hydrogenatedC5/cycloaliphatic resins; fully or partially hydrogenatedC5/cycloaliphatic/styrene/C9 resins; fully or partially hydrogenatedcycloaliphatic resins; and combinations thereof. Exemplary commercialhydrocarbon resins include Regalite™ hydrocarbon resins (EastmanChemical Co., Kingsport, Tenn., US).

In various embodiments, the adhesives comprise at least about 1, 2, 5,8, or 10 and/or not more than about 40, 30, 25, or 20 weight percent ofat least one processing oil. Moreover, in such embodiments, theadhesives comprise in the range of about 2 to 40, 5 to 30, 8 to 25, orabout 10 to 20 weight percent of at least one processing oil. Suitableprocessing oils are those known in the art, and include, for example,mineral oils, naphthenic oils, paraffinic oils, aromatic oils, castoroils, rape seed oil, triglyceride oils, or combinations thereof. As oneskilled in the art would appreciate, processing oils may also includeextender oils, which are commonly used in adhesives. The use of oils inthe adhesives are in some instances desirable if the adhesive is to beused as a pressure-sensitive adhesive (PSA) to produce tapes or labelsor as an adhesive to adhere nonwoven articles. In certain additionalembodiments, the adhesive comprises no processing oils.

In various embodiments, the adhesives comprise at least about 1, 2, 5,8, or 10 and/or not more than about 40, 30, 25, or 20 weight percent ofat least one wax. Moreover, in such embodiments, the adhesives comprisein the range of about 1 to 40, 5 to 30, 8 to 25, or 10 to 20 weightpercent of at least one wax. Suitable waxes can include those known inthe art, for example, microcrystalline wax, paraffin wax, waxes producedby Fischer-Tropsch processes, functionalized waxes (maleated, fumerated,or wax with functional groups etc.) and vegetable wax. The use of waxesin the adhesives are desirable in certain instances if the adhesive isto be used as a hot melt packaging adhesive. In certain embodiments, theadhesive comprises no wax.

In various embodiments, the adhesives comprise at least about 0.1, 0.5,1, 2, or 3 and/or not more than about 20, 10, 8, or 5 weight percent ofat least one antioxidant. Moreover, in such embodiments, the adhesivescomprise in the range of about 0.1 to 20, 1 to 10, 2 to 8, or 3 to 5weight percent of at least one antioxidant. In other embodiments, theadhesive contains no antioxidant.

In various embodiments, the adhesives comprise at least about 0.5, 1, 2,or 3 and/or not more than about 20, 10, 8, or 5 weight percent of atleast one plasticizer. Moreover, in such embodiments, the adhesivescomprise in the range of about 0.5 to 20, 1 to 10, 2 to 8, or 3 to 5weight percent of at least one plasticizer. Suitable plasticizers arethose known in the art, and include, for example, dibutyl phthalate,dioctyl phthalate, chlorinated paraffins, and phthalate-freeplasticizers. Commercial plasticizers include, for example, Benzoflex™and Eastman 168™ plasticizers (Eastman Chemical Co., Kingsport, Tenn.,US).

In various additional embodiments, the adhesives comprise at least about10, 20, 30, or 40 and/or not more than about 90, 80, 70, or 55 weightpercent of at least one filler. Moreover, in such embodiments, theadhesives comprise in the range of about 1 to 90, 20 to 80, 30 to 70, or40 to 55 weight percent of at least one filler. Suitable fillers arethose known in the art and include, for example, carbon black, clay andother silicates, calcium carbonate, titanium oxide, zinc oxide, orcombinations thereof.

Rubber Compositions Comprising Silane-Functionalized Resins

Disclosed are also various rubber compositions for use in, for example,automotive components, such as, but not limited to, tires and tirecomponents, automotive belts, hoses, brakes, and the like, as well asnon-automotive and/or mechanical devices including technical rubberarticles such as, for example, belts, as in conveyor belts, forinstance, straps, brakes, and hoses or tubing, and the like, as well asclothing articles, such as, but not limited to, shoes, boots, slippers,and the like, that incorporate the disclosed functionalized resins. Thedisclosed silane-functionalized resins can act as a processing aidduring mixing of rubber Formulations by associating with the silicasurface. The functionalization of the silica surface can be comparedwith other commercially available silanes for rubber compounding (FIG.2A) except that the embodiment described involves one to many silanefunctionalities covalently attached to a polymer or resin structurethrough polar group containing linkages (FIG. 2B). In FIG. 2A, theelement 110 corresponds to polymers and 100B corresponds to resin. Thisis a theoretical depiction of the normal arrangement found in suchcompositions using non-functionalized resins. In FIG. 2B, there is shownagain element 110 corresponding to the polymer, and element 100Bcorresponding to the resin, as well as element 100A corresponding to alinker, as contemplated herein. That is, in FIG. 2B, elements 100A and100B together are equivalent in the schematic diagram to Formula I,wherein “resin” in Formula I corresponds to part 100B and the remainderof the Formula I equation, i.e.—[Z_(k)—X_(n)—R¹—(CH₂)_(m)—Si(R²)_(p)]_(q), corresponds to element 100Ain FIG. 2B.

Thus, rubber compositions are disclosed that comprise elastomers,fillers, and the silica-functionalized resins disclosed herein. Theelastomer can be one or more of a natural rubber, a polyisoprene, astyrene-butadiene rubber, a polybutadiene, a halobutyl rubber, and anitrile rubber, or a functionalized rubber grade, or a rubber mixturethereof. In another particular embodiment, the halobutyl rubber isbromobutyl rubber, chlorobutyl rubber, a functionalized rubber grade, ora mixture thereof. When used in tires, the main rubber componentcomprises various polymers such as, but not limited to, polyisoprene(synthetic or natural), styrene-butadiene copolymer, or butadienepolymer, and the like. Such rubber polymer(s) can contain variousmodifications and/or functionalizations at the end of chains or atpendant positions along the polymer chain. These modifications cancontain various standard moieties such as, but not limited to, hydroxyl-and/or ethoxy- and/or epoxy- and/or siloxane- and/or amine- and/oraminesiloxane- and/or carboxy- and/or phthalocyanine- and/orsilane-sulfide-groups, and/or combinations thereof. Additionalmodifications known to one of skill, such as metal atoms, can also beincluded in the rubber polymers used to make the disclosed tires andother rubber-containing components disclosed herein.

The rubber mixture according to the disclosure also contains 5 to 80phr, preferably 5 to 49 phr, particularly preferably 5 to 30 phr, andmore particularly preferably 5 to 20 phr of at least one further dienerubber.

The at least one further rubber is in this case one or more of naturalpolyisoprene and/or synthetic polyisoprene and/or butadiene rubberand/or solution-polymerized styrene-butadiene rubber and/oremulsion-polymerized styrene-butadiene rubber and/or liquid rubbers witha molecular weight Mw greater than 20,000 g/mol and/or halobutyl rubberand/or polynorbornene and/or isoprene-isobutylene copolymer and/orethylene-propylene-diene rubber and/or nitrile rubber and/or chloroprenerubber and/or acrylate rubber and/or fluorine rubber and/or siliconerubber and/or polysulfide rubber and/or epichlorohydrin rubber and/orstyrene-isoprene-butadiene terpolymer and/or hydrated acrylonitrilebutadiene rubber and/or isoprene-butadiene copolymer and/or hydratedstyrene-butadiene rubber.

In particular, nitrile rubber, hydrated acrylonitrile butadiene rubber,chloroprene rubber, butyl rubber, halobutyl rubber, orethylene-propylene-diene rubber are used in the production of technicalrubber articles such as straps, belts, and hoses.

In another embodiment, the further diene rubber is one or more ofsynthetic polyisoprene and natural polyisoprene and polybutadiene.Preferably, the further diene rubber is at least natural polyisoprene.This allows to achieve particularly favorable processability(extrudability, miscibility, et cetera) of the rubber mixture.

According to a further embodiment of the disclosure, the rubber mixturecontains 10 to 70 phr of a conventional solution-polymerizedstyrene-butadiene rubber having a glass transition temperature of −40 to+10° C. (high-Tg SSBR) and 10 to 70 phr of the styrene-butadiene rubberhaving a Tg of −120 to −75° C., preferably −110 to −75° C., particularlypreferably −110 to −80° C., and most particularly preferably −87 to −80°C., with the rubber in this embodiment preferably having a styrenecontent of 1 to 12 wt %, particularly preferably 9 to 11 wt %, and mostparticularly preferably 10 to 11 wt %.

The rubber mixture can also contain at least one further diene rubber,in particular natural and/or synthetic polyisoprene.

When used in tire mixtures a resin as described above can be used as thebase resin to be functionalized. The polar linker has an increasedbonding strength to the reactive sites of the filler material, i.e., tothe hydroxyl groups of silica or to the reactive surface sites of otherfiller by providing corresponding functional groups that are compatibleto the reaction centers of the other fillers. Thus, the disclosure isnot limited to silica as a filler material and other fillers, such ascarbon black.

The disclosed silane functionalized resins can be incorporated into therubber mixtures by various methods known to one of skill. For instance,1 to 100 mol % of monomers, 2 to 70 mol % of monomers, 5 to 50 mol % ofmonomers bearing the described functional groups as end capped and/orpendant functionalization can be incorporated into the rubber mixtures.The amount of functionalized resin in the rubber mixture can be from 5to 400 phr, 10 to 375 phr, 10 to 350 phr, 10 to 325 phr, 10 to 300 phr,10 to 275 phr, 10 to 250 phr, 10 to 225 phr, 10 to 200 phr, 10 to 175phr, 10 to 150 phr, 10 to 125 phr, or 10 to 100 phr. The rubber mixturecan additionally comprise unfunctionalized resins. Further, mixtures offunctionalized and unfunctionalized resins can be incorporated into therubber mixtures. The total resin content, including unfunctionalizedresin and functionalized resin, can be from 5 to 400 phr, 5 to 350 phr,10 to 300 phr, 10 to 275 phr, 10 to 250 phr, 10 to 225 phr, 10 to 200phr, 10 to 175 phr, 10 to 150 phr, 10 to 125 phr, or 10 to 100 phr, i.e.a highly pendant-functionalized resin can be incorporated into therubber mixtures to achieve a phr value of 5 to 50 by dilution. Likewise,mixtures of end-capped and pendant functionalized resins can beincorporated into the rubber mixtures by adding the desired amount tothe rubber mixture to achieve the desired phr.

According to another embodiment, the amount of the solution-polymerizedstyrene-butadiene rubber present in the rubber mixture can be from 5 to50 phr, 20 to 50 phr, or even 30 to 40 phr. The rubber mixture of thedisclosure comprises 20 to 250 phr, preferably 30 to 150 phr,particularly preferably 30 to 85 phr, of at least one filler. The fillercan be one or more of a polar or non-polar filler, such as silica,carbon black, alumino-silicates, chalk, starch, magnesium oxide,titanium dioxide, and/or rubber gels, or mixtures thereof. Further,carbon nanotubes (CNTs) including hollow carbon fibers (HCF) andmodified CNTs, including one or more functional groups such as, forexample, hydroxy, carboxy, or carbonyl groups, can also be used asfiller materials. Additionally, graphite and graphene, as well as“carbon-silica dual-phase filler” can be used as filler materials. It ispossible here to use any of the types of carbon black known to theperson skilled in the art.

In some embodiments, the rubber mixture comprises carbon black as solefiller or as main filler, that is, the amount of carbon black ismarkedly greater than the amount of any other fillers present. Ifanother filler is present in addition to carbon black, it is preferablethat the additional filler is silica. It is therefore also conceivablethat the rubber mixture of the invention comprises similar amounts ofcarbon black and silica, for example 20 to 100 phr of carbon blackcombined with 20 to 100 phr of silica. For example, the ratio of carbonblack to silica can be anywhere from about 1:150 to 100:20.

In some embodiments, the rubber mixture comprises silica as sole filleror as main filler, that is, the amount of silica is markedly greaterthan the amount of any other fillers present.

Particularly good rolling resistance indicators (rebound resilience at70° C.) and tear properties are thus achieved for the application invehicle tires.

When carbon black is present as the filler, preferably the amount ofcarbon black in the rubber mixture is from 1 to 150 phr, 2 to 100 phr, 2to 90 phr, 2 to 80 phr, 2 to 70 phr, 2 to 60 phr, 2 to 50 phr, 2 to 40phr, 2 to 30 phr, or more preferably from 2 to 20 phr. However, it ispreferable to use a carbon black which has an iodine adsorption numberaccording to ASTM D 1510 of 30 to 180 g/kg, preferably 40 to 180 g/kg,particularly preferably 40 to 130 g/kg, and a DBP number according toASTM D 2414 of 80 to 200 ml/100 g, preferably 90 to 200 ml/100 g,particularly preferably 90 to 150 ml/100 g.

The silicas can be silicas known to the person skilled in the art thatare suitable as fillers for tire rubber mixtures. For instance, onenon-limiting embodiment includes a finely dispersed, precipitated silicahaving a nitrogen surface area (BET surface area) (according to DIN ISO9277 and DIN 66132) of 35 to 350 m²/g, preferably 35 to 260 m²/g,particularly preferably 100 to 260 m²/g, and most particularlypreferably 130 to 235 m2/g and a CTAB surface area (according to ASTM D3765) of 30 to 400 m²/g, preferably 30 to 250 m²/g, particularlypreferably 100 to 250 m²/g, and most particularly preferably 125 to 230m²/g. Such silicas, when used, for example, in rubber mixtures for tiretreads, produce particularly favorable physical properties of thevulcanizate. This can also provide advantages in mixture processing byreducing mixing time while retaining the same product properties, whichleads to improved productivity. As silicas, one can both use, forexample, those of the Ultrasil® VN3 type (Evonik Industries AG, Essen,Germany) and highly-dispersible silicas such as the aforementioned HDsilicas (for example, Zeosil® 1165 MP Rhodia-Solvay InternationalChemical Group, Brussels, Belgium).

To improve processability and to bind the silica and other polar fillersthat are in some embodiments present to the diene rubber, silanecoupling agents are used in various embodiments of the described rubbermixtures. In such embodiments, one or a plurality of different silanecoupling agents in combination with one another are used. The rubbermixture in some embodiments therefore contain a mixture of varioussilanes. The silane coupling agents react with the superficial silanolgroups of the silica or other filler polar groups, such as the polarfillers disclosed above, during the mixing of the rubber or of therubber mixture (in situ), or even before adding the filler to the rubberas a pretreatment (pre-modification). In such embodiments, the silanecoupling agents are any of those known to the person skilled in the artas suitable for use in the disclosed rubber mixtures. Non-limitingexamples of conventional coupling agents are bifunctional organosilanespossessing at least one alkoxy, cycloalkoxy, or phenoxy group on thesilicon atom as a leaving group, and as the other functionality, havinga group that can optionally undergo a chemical reaction with the doublebonds of the polymer after splitting. The latter group, in someembodiments, for example, constitute the following chemical groups: SCN,—SH, —NH₂ or —Sγ— (where γ is from 2 to 8).

Contemplated silane coupling agents for use in such embodiments includefor example, 3-mercaptopropyltriethoxysilane,3-thiocyanato-propyl-trimethoxysilane, or3,3′-bis(triethoxysilylpropyl)-polysulfide with 2 to 8 sulfur atoms suchas, for example, 3,3′-bis(triethoxysilylpropyl)tetrasulfide (TESPT), thecorresponding disulfide (TESPD), or mixtures of the sulfides with 1 to 8sulfur atoms having a differing content of the various sulfides. Forexample, TESPT can also be added as a mixture with industrial carbonblack (X50S®, Evonik Industries AG, Essen, Germany).

In another embodiment, a silane mixture is used that contains up to 40to 100 wt % of disulfides, particularly preferably 55 to 85 wt % ofdisulfides, and most particularly preferably 60 to 80 wt % ofdisulfides. This type of mixture, described by way of example in U.S.Pat. No. 8,252,863, is obtainable by way of example with Si 261® (EvonikIndustries AG, Essen, Germany). Blocked mercaptosilanes such as thoseknown from WO 99/09036 can also be used as silane coupling agents.Silanes such as those described in U.S. Pat. Nos. 7,968,633; 7,968,634;7,968,635; and, 7,968,636, as well as U.S. Pat. App. Pub. Nos U.S. Pat.App. Pub. Nos. 20080161486; 20080161462; and 20080161452, or anycombination thereof, may also be used. Suitable silanes are also, forexample, the silanes marketed under the name NXT in different variantsby the firm Momentive, USA, or those marketed under the name VP Si 363®by the firm Evonik Industries.

Moreover, it is possible for the rubber mixture to contain carbonnanotubes (CNTs), including discrete CNTs, so-called hollow carbonfibers (HCFs), and modified CNT containing one or a plurality offunctional groups such as hydroxy, carboxy, and carbonyl groups.

Graphite, graphene, and so-called “carbon-silica dual-phase fillers” arealso suitable as fillers.

Moreover, the rubber mixture can contain other polar fillers, such as,for example, aluminosilicates, chalk, starch, magnesium oxide, titaniumdioxide, or rubber gels.

In one embodiment, the rubber mixture is free from other fillers, thatis, in this embodiment the rubber mixture comprises 0 phr of any otherfiller. In this embodiment, it is therefore not necessary to add anysecond filler.

For the purposes of the present disclosure, zinc oxide is not consideredto be a filler.

In one embodiment, the rubber mixture contains 0 to 70 phr, 0.1 to 60phr, or 0.1 to 50 phr of at least one plasticizer. These include one ormore of all plasticizers known to the person skilled in the art, such asaromatic, naphthenic, or paraffinic mineral oil plasticizers, forexample, MES (mild extraction solvate) or TDAE (treated distillatedaromatic extract), rubber-to-liquid (RTL) oils or biomass-to-liquid(BTL) oils, factices, plasticizing resins, or liquid polymers (such asliquid BR), whose average molecular weight (determined by gel permeationchromatography (GPC), based on BS ISO 11344:2004), is between 500 and 20000 g/mol. If liquid polymers are used in the rubber mixture accordingto the invention as plasticizers, these are not included as rubber incalculating the composition of the polymer matrix.

In embodiments in which a mineral oil is used, the mineral oil isselected from one or more of DAE (distillated aromatic extracts) and/orRAE (residual aromatic extracts) and/or TDAE (treated distillatedaromatic extracts) and/or MES (mild extracted solvents) and/ornaphthenic oils and/or paraffinic oils.

Moreover, the rubber mixtures disclosed herein can contain commonadditives in the common number of parts by weight. These additivesinclude:

-   -   a) antioxidants such as, for example,        N-phenyl-N′-(1,3-dimethylbutyl)-p-phenylene diamine (6PPD),        N,N′-Diphenyl-p-phenylene diamine (DPPD),        N,N′-ditolyl-p-phenylene diamine (DTPD),        N-Isopropyl-N′-phenyl-p-phenylene diamine (IPPD),        N,N′-Bis(1,4-dimethylpentyl)-p-phenylenediamine (77PD), and        2,2,4-trimethyl-1,2-dihydroquinoline (TMQ),    -   b) activators such as, for example, zinc oxide and fatty acids        (for example, stearic acid),    -   c) waxes,    -   d) functionalized and non-functionalized resins, in particular        adhesive tackifier resins, such as rosin, and the like,    -   e) mastication auxiliaries such as, for example,        2,2′-dibenzamidodiphenyldisulfide (DBD), and    -   f) processing auxiliaries, for example, fatty acid salts such        as, for example, zinc soaps, fatty acid esters and derivatives        thereof.

In particular, in the use of the rubber mixtures disclosed herein forthe internal components of a tire or a technical rubber article that arein direct contact with the reinforcing supports present, a suitableadhesive system, often in the form of adhesive tackifier resins, is alsogenerally added to the rubber.

The proportion of further additives contained in the entire amount is 3to 150 phr, preferably 3 to 100 phr, and particularly preferably 5 to 80phr.

The proportion of further additives contained in the entire amount alsoincludes 0.1 to 10 phr, preferably 0.2 to 8 phr, and particularlypreferably 0.2 to 4 phr of zinc oxide (ZnO).

This zinc oxide can be of any type known to the person skilled in theart, such as, for example, ZnO granulate or powder. Generally speaking,conventionally used zinc oxide shows a BET surface area of less than 10m²/g. However, so-called nano zinc oxide having a BET surface area of 10to 60 m²/g can also be used.

Vulcanization is performed in the presence of sulfur or sulfur donorsusing vulcanization accelerators, with some vulcanization acceleratorsalso being capable of acting as sulfur donors. Sulfur, or sulfur donors,and one or a plurality of accelerators, are added in the last mixingstep in the aforementioned amounts to the rubber mixture. Here, theaccelerator is one or more of thiazole accelerators and/or mercaptoaccelerators and/or sulfenamide accelerators and/or thiocarbamateaccelerators and/or thiuram accelerators and/or thiophosphateaccelerators and/or thiourea accelerators and/or xanthogenateaccelerators and/or guanidine accelerators.

A sulfenamide accelerator selected from N-cyclohexyl-2-benzothiazolesulfenamide (CBS) and/or N,N-dicyclohexylbenzothiazole-2-sulfenamide(DCBS) and/or N-tert-butyl-2-benzothiazyl sulfenamide (TBBS) can beused.

Suitable accelerators include, for instance those selected fromN-cyclohexyl-2-benzothiazole sulfenamide (CBS) and/orN,N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS),N-tert-butyl-2-benzothiazyl sulfenamide (TBBS), mercapto benzothiazole,tetramethyl thiuram disulfide, benzothiazole disulfide, diphenylguanidine, zinc dithiocarbamate, alkylphenol disulfide, zinc butylxanthate, N-dicyclohexyl-2-benzothiazolesulfenamide,N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylenebenzothiazole-2-sulfenamide, N,N-diphenyl thiourea, dithiocarbamylsulfenamide, N,N-diisopropyl benzothiozole-2-sulfenamide,zinc-2-mercapto toluimidazole, dithio bis(N-methyl piperazine), dithiobis(N-beta-hydroxy ethyl piperazine), dithio bis(dibenzyl amine), andcombinations thereof. Other vulcanizing accelerators include, forexample, thiuram, and/or morpholine derivatives.

In one embodiment of the disclosed rubber mixtures, the mixturecomprises CBS as the accelerator. Particularly good tear properties arethus achieved for such rubber mixtures.

Further, network-forming systems such as for example those availableunder the brand names Vulkuren® (Lanxess, Shanghai, PRC), Duralink®(ChemLink, Schoolcraft, Mich., US), and Perkalink® (Lanxess, Shanghai,PRC), or network-forming systems such as those described in WO2010/059402, can also be used in the rubber mixture. This systemcontains a vulcanizing agent that crosslinks with a functionalitygreater than four and at least one vulcanization accelerator. Thevulcanizing agent that crosslinks with a functionality greater than fourhas, for example, General Formula A:

G[C_(a)H_(2a)CH₂—S_(b)Y]_(c)  A

where G is a polyvalent cyclic hydrocarbon group and/or a polyvalentheterohydrocarbon group and/or a polyvalent siloxane group that contains1 to 100 atoms; where each Y contains sulfur-containing functionalitiesindependently selected from a rubber-active group; and where a, b, and care whole numbers each of which are independently selected from thefollowing: a equals 0 to 6; b equals 0 to 8; and c equals 3 to 5.

The rubber-active group is one or more of a thiosulfonate group, adithiocarbamate group, a thiocarbonyl group, a mercapto group, ahydrocarbon group, and a sodium thiosulfonate group (colored saltgroup). This allows achievement of highly favorable abrasion and tearproperties of the rubber mixture according to the invention.

Within the scope of the present disclosure, sulfur and sulfur donors,including sulfur-donating silanes such as TESPT, curing agents and curessuch as those described in EP 2288653, vulcanization accelerators asdescribed above, and vulcanizing agents that crosslink with afunctionality of greater than 4 as described in WO 2010/059402, such as,for example, a vulcanizing agent of Formula A), and the aforementionedsystems Vulkuren® (Lanxess, Shanghai, PRC), Duralink® (ChemLink,Schoolcraft, Mich., US), and Perkalink® (Lanxess, Shanghai, PRC), arecombined under the term vulcanizing agents.

The rubber mixture according to the disclosure can include at least oneof these vulcanizing agents. This makes it possible to producevulcanizates, in particular for use in vehicle tires, from the rubbermixture according to the disclosure.

In some embodiments, vulcanization retarders are also present in therubber mixture. As known in the art, there is typically a “trade off”between rolling resistance and wet braking in tire technology. Oftenwhen one of these two elements is improved, the other is worsened. Thus,an improvement in rolling resistance (RR) is often accompanied by aworsened performance of wet braking, and vice versa. This is the RR-wetbraking target conflict. Embodiments encompassed by this disclosuretherefore include tires that possess surprisingly improved rollingresistance with no change in wet braking. Thus, an object of thedisclosed rubber compositions is to provide a vehicle tire that exhibitsimproved rolling resistance behavior, as well as snow performance. Thisobject is achieved in that the vehicle tire contains the rubber mixturesaccording to this disclosure in at least one component as describedabove. In this context, all of the aforementioned embodiments of theconstituents and properties thereof apply.

A further object of the disclosed rubber compositions is to provide avehicle tire that exhibits improved rolling resistance behavior andimproved tear properties, in particular increased tear propagationresistance. This object is achieved in that the vehicle tire containsthe rubber mixtures according to this disclosure in at least onecomponent as described above. In this context, all of the aforementionedembodiments of the constituents and properties thereof apply.

In one embodiment, the component is a tread. As known to the personskilled in the art, the tread contributes to a relatively high degree tooverall rolling resistance of the tire. In particular, high resistanceto cracking and crack propagation in the tread is also advantageous. Inone embodiment, the rubber compositions described herein are useful inother parts of the tire as well and can comprise various tire componentsand various tire component compounds. The tires can be built, shaped,molded and cured by various methods that are known and will be readilyapparent to those having skill in such art.

Another object of the present disclosure is improving the rollingresistance performance and the tear properties of vehicle tires.According to the disclosure, this object is achieved through the use ofthe rubber mixtures described above with all embodiments and features invehicle tires, in particular in the tread of a vehicle tire, and/or abody mixture of a vehicle tire.

A further object of the disclosure is to optimize the abrasion behaviorand the tear properties of technical rubber articles such as, forexample, belts, straps, brakes, and hoses without having a significantnegative effect on other properties that are relevant for the respectiveuse.

This object is achieved by using the above-described rubber mixtures forthe production of technical rubber articles such as, for example, belts(for instance, conveyor belts, automobile engine belts such as timingbelts, driving belts, and the like), straps, seals, tubes, and hoses.Another such technical rubber article is a shoe sole, for instance forwalking shoes, running shoes, cross-training shoes, boots, slippers,etc., items that are to be worn on the feet to protect the feet andassociated bones and joints from damage caused by jarring or poundingmotions associated with walking, running, jumping, etc. and to provideexcellent resistant to slipping in wet and/or dry conditions. Variousmethods are known in the art for incorporation of rubber mixtures intofootwear. See, for example, U.S. Pat. App. Pub. Nos.: 2013/0291409,2011/0252671, and U.S. Pat. No. 8,689,381 (all of which are incorporatedherein by reference in their entirety for all purposes).

The term body mixture as used here refers to rubber mixtures for theinternal components of a tire. Internal tire components essentiallyinclude the squeegee, side wall, inner liner (inner layer), coreprofile, belt, shoulder, belt profile, carcass ply, bead wire, cableprofile, horn profile, and bandage.

Manufacturing of these disclosed rubber mixtures is performed by themethods commonly used in the rubber industry, in which a basic mixturewith all of the constituents except the vulcanization system (sulfur andvulcanization-affecting substances) is first produced in one or aplurality of mixing stages. The finished mixture is produced by addingthe vulcanization system in a last mixing stage. The finished mixture isfurther processed, for example, by means of an extrusion process, andgiven the corresponding form.

For use in vehicle tires, the mixture is preferably made into a treadand applied in the known manner in production of the vehicle tire blank.However, the tread can also be wound onto a tire blank in the form of anarrow rubber mixture strip. In two-part treads (upper part: cap andlower part: base), the rubber mixture according to the disclosure can beused both for the cap and for the base.

Manufacturing of the rubber mixture according to the disclosure for useas a body mixture in vehicle tires is performed as described above forthe tread. The difference lies in the molding after the extrusionprocess. The forms of the rubber mixture according to the disclosureobtained in this manner for one or a plurality of various body mixturesare then used to produce a tire blank. To use the rubber mixtureaccording to the disclosure in belts and straps, in particular inconveyor belts, the extruded mixture is made into the corresponding formand, at the same time or thereafter, often provided with reinforcingsupports, for example, synthetic fibers or steel cords. In most cases,one obtains a multilayer structure composed of one and/or a plurality oflayers of the rubber mixture, one and/or a plurality of layers of thesame and/or different reinforcing supports, and one and/or a pluralityof further layers of the same and/or another rubber mixture.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art. Although methods and materials similar or equivalent to thosedescribed herein can be used in the practice or testing of the presentinvention, suitable methods and materials are described below. Allpublications, patent applications, patents, and other referencesmentioned herein are incorporated by reference in their entirety for allpurposes. In case of conflict, the present specification, includingdefinitions, will control. In addition, the materials, methods, andexamples are illustrative only and not intended to be limiting.

EXAMPLES

A variety of functionalized resins have been prepared and tested inrubber mixtures for vehicle tires and prepared and tested in othercompositions, such as adhesives and the like. The synthetic routes andthe experimental data are provided below.

Example 1: Silane Resin Functionalization by Modification of PolarLinkers

In the following examples, various resins are functionalized with silanemoieties as described below. The functionalized resins can besynthesized using the different methodologies provided hereinbelow, aswell as other methodologies apparent to one of skill in the art uponreading the methods provided below. All chemical reagents were fromSigma-Aldrich (St. Louis, Mo., US), unless otherwise noted.

Example 1.1—Synthesis of Pendant Silane-Containing Resin ViaAcetoxystyrene Functionalization

Steps 1A through 1C show the synthesis of pendant silane-containingresin by functionalization of acetoxystyrene. Particularly, Scheme 1shows an embodiment of the ether route for deprotection ofacetoxystyrene-based resin to phenol, followed by ether formation, andsilane functionalization at an internal, pendant position within theresin. Note that in the following Schemes 1 through 5, where thevariables “r” and “q” appear, the representation on the left is of thefunctionalization moiety, not the entire resin backbone. In other words,the starting materials represented in these schemes are representativeof the many points at which the resin backbone is derivatized, the resinbackbone not being present or depicted in the Schemes themselves, butare implied. The derivatization occurs randomly throughout the entireresin backbone. The starting material representations do not indicate ablock copolymer, or that block copolymer methods were used in thesestrategies, though such strategies are known and can be employed inthese Examples instead of the methodologies set forth below. Exemplarystarting reagent and end product embodiments of this synthetic route arealso depicted in FIG. 1A.

Step 1A: Synthesis of Pendant Phenol-Functionalized Resin fromAcetoxystyrene Deprotection

To modify acetoxystyrene-containing resins in Step A, phenoldeprotection of acetoxystyrene-modified resin was achieved by using baseto remove the acetoxy groups. In a one-necked, 1 L round-bottom flask(RBF), a stir bar and 110.3 g of 3.4 mol % acetoxystyrene-containingresin (0.957 mol containing 0.0324 mol of acetoxystyrene units) werecharged. Tetrahydrofuran (THF, 600 mL) was added. The solution wasstirred at 500 rpm. A solution of 3.9 g of sodium hydroxide (0.0975 mol)was prepared in 20.4 mL of deionized water. When the starting materialresin fully dissolved, the solution of sodium hydroxide was added.Triethylamine (TEA, 16.4 g, 0.162 mol) was added, and the RBF was fittedwith a condenser. The solution was heated to reflux for 4 to 5 hours.The reaction was monitored by FT-IR. The reaction was consideredcomplete when the carbonyl band (1750 cm ¹) fully disappeared. Heatingwas stopped. The flask was allowed to cool to room temperature. THF wasevaporated. Dichloromethane (DCM, 600 mL) was added to the RBF, and thesolution was stirred vigorously. The solution was then transferred intoa separatory funnel. The organic layer was washed with 2×600 mL ofaqueous HCl (1 mol/L) and then 4×600 mL of deionized water. The organiclayer was dried over magnesium sulfate. The solid was filtered, and thefiltrate was kept. The DCM was evaporated, and the product was dried at40° C. under reduced pressure until constant weight. The final yield was102.2 g (94% of the theoretical yield). Sample Fouriertransform-infrared spectra (FT-IR) of the resultant product is shown inFIG. 3. Sample TGA and DSC spectra of Step 1A deprotection product areprovided in FIG. 4 and FIG. 5, respectively.

Step 1B: Synthesis of Pendant Carboxylic Acid-Functionalized Resin fromPhenol Group Functionalization

In a 1-necked, 2 L round-bottom flask, 95.2 g of 3.38 mol %phenol-functionalized resin (836.5 mmol containing 28.3 mmol of phenolunits) and 839 mL of acetone were charged. The mixture was stirred untilthe resin fully dissolved. Then, 4.58 g of potassium iodide (27.6 mmol),2.27 g of sodium hydroxide (56.8 mmol), and 16.7 g of sodiumchloroacetate (143.4 mmol) were added. The flask was fitted with areflux condenser and heated with an oil bath to 58° C. for 18 hours. Thesolvent was removed. The viscous material was dissolved in 700 mL ofDCM. The obtained slurry was added to 700 mL of aqueous HCl 1M solution.The two-phase system was stirred until complete dissolution of the solidmaterials, and the aqueous layer was discarded. The organic phase waswashed with aqueous HCl 1M solution, followed by aq NaOH 1M solution,and then washed a last time with aqueous HCl 1M solution. The procedurewas repeated, and the aqueous layer was discarded each time. Then, theorganic phase was washed an additional 4 times as needed with aqueousHCl 1 M solution. The organic layer was separated and dried overanhydrous MgSO₄. MgSO₄ was removed by gravimetric filtration over filterpaper, and the filtrate was kept. Solvent was removed, and the productwas dried under reduced pressure at room temperature overnight. Theobtained solid weighed 86.7 g (90% of the theoretical yield). SampleFT-IR of the resultant product is shown in FIG. 6. Sample TGA and DSCspectra of Step 1B product are provided in FIG. 7 and FIG. 8,respectively.

Step 1C: Synthesis of Pendant Silane-Functionalized Resin fromCarboxylic Acid Group Functionalization

In a 3-necked, 2 L round-bottom flask fitted with a thermometer and astir bar, 83.0 g of 3.38 mol % carboxylic acid containing resin (717mmol containing 24.2 mmol of carboxyl units) and 715 mL of DCM werecharged. The solution was placed under a N₂ blanket and magneticallystirred. When the resin was fully dissolved, the flask was chilled withan ice/NaCl/water bath. When the temperature reached 2.5±2.5° C., 2.69 gof ethyl chloroformate (24.8 mmol) followed by 2.46 g of TEA (24.3 mmol)were added. The activation time (formation of mixed anhydride) was 30min at 5±3° C. Then, 5.38 g of 3-aminopropyltriethoxysilane (24.3 mmol)was charged. The chilling bath was removed, and the solution was allowedto warm to room temperature and continue reaction for 23 hours. Thereaction solution was dried over anhydrous MgSO₄. The solid was removedby gravimetric filtration over Whatman® #1 filter paper. The solvent wasremoved, and 50 mL of anhydrous reagent alcohol was added to the flask.The solvent was decanted, and the waxy product was washed one more timewith 50 mL of anhydrous reagent alcohol. The product was dried underreduced pressure at room temperature for over 48 hours. The productweighed 81.0 g (92% of the theoretical yield). Silica incorporation wasconfirmed as 5500 parts per million (ppm) using a xylenesinductively-coupled plasma (ICP) digestion method. Sample FT-IR of theresultant product is shown in FIG. 9. Sample TGA, DSC, and GPC spectraof Step 1C product are provided in FIGS. 10, 11, and 12, respectively.

Example 1.2: Synthesis of End-Capped Silane-Containing Resin Via PhenolFunctionalization

Scheme 2 shows a similar embodiment of the ether route for deprotectionof acetoxystyrene-based resin to phenol, followed by ether formation,and silane functionalization, but instead of the functionalizationoccurring at an internal, pendant position within the resin, the silanefunctionalization is added to the end cap, terminal, position of theresin. In this embodiment, the phenol groups were functionalized withcarboxylic acid groups via reaction of phenol, sodium hydroxide, sodiumchloroacetate, and potassium iodide catalyst. Exemplary starting reagentand end product embodiments of this synthetic route are also depicted inFIG. 1B.

Step 2A: Synthesis of End-Capped COOH-Functionalized Resin from PhenolGroup Functionalization

In a 3-necked, 2 L round-bottom flask fitted with a mechanical stirrerand reflux condenser, 100.6 g of 10.8 mol % phenol-functionalized resin(902 mmol containing 97.2 mmol of phenol units) and 1.50 L of acetonewere charged. When the resin was fully dissolved with stirring, 10.55 gof potassium iodide, 6.48 g of sodium hydroxide, and 101.1 g of sodiumchloroacetate were added. The reaction solution was heated to 57° C. for18 hours. Solvent was removed, and the product was dissolved in 3 L ofDCM and washed with 1.2 L of 1M aqueous HCl. The two-phase solution wasstirred until complete dissolution of all solids. The aqueous layer wasdiscarded. The solution was washed with 1M aqueous HCl, 1M aqueous NaOH,and then 1M aqueous HCl. The procedure was repeated and washed with 1Maqueous HCl four more times as needed. The organic phase was dried overanhydrous MgSO₄. MgSO₄ was removed by gravimetric filtration over filterpaper. Solvent was removed, and the product was dried in under reducedpressure at room temperature overnight. The product weighed 103.8 g (98%of the theoretical yield). Sample FT-IR of the resultant product isshown in FIG. 13. Sample TGA and DSC spectra of Step 2A product areprovided in FIGS. 14 and 15, respectively.

Step 2B: Synthesis of End-Capped Silane-Functionalized Resin from COOHGroup Functionalization

In a 3-necked, 3 L round-bottom flask fitted with a thermometer and astir bar, 106.0 g of 10.8 mol % carboxylic acid containing resin (900mmol containing 97.0 mmol of carboxyl units), and 2.70 L of DCM werecharged. The solution was placed under a N₂ blanket and magneticallystirred. When the resin was fully dissolved, the flask was chilled withan ice/NaCl/water bath. When the temperature reached 2.5±2.5° C., 10.75g of ethyl chloroformate (99.1 mmol) followed by 9.97 g of TEA (98.5mmol) were added. The activation time (formation of mixed anhydride) was32 min at 5±3° C. Then, 21.58 g of 3-aminopropyltriethoxysilane (97.5mmol) was charged. The chilling bath was removed, and the reaction wasallowed to warm to room temperature. The reaction was allowed tocontinue 25 hours at room temperature. Insoluble (triethylaminehydrochloride) was removed by gravimetric filtration over Whatman® #1filter paper. Then, 300 mL of hexanes was added. The mixture was stirredfor 30 minutes and stored in the freezer for 48 hours. The two-phasesystem was allowed to warm to room temperature. The top hexanes layerwas isolated, and solvent was removed. The product was dried underreduced pressure at room temperature for 2 to 3 days. Dry ethanol wasused to help remove hexanes. The waxy product weighed about 80 g (63-64%of the theoretical yield). An alternative workup is to remove allsolvent under reduced pressure after the reaction is complete anddissolve the product in diethyl ether or methyl tertiary butyl ether(MTBE). The solution is then filtered over filter paper to removetriethylamine hydrochloride byproduct, and the solvent is slowlyevaporated. The product is dried at room temperature under reducedpressure. ICP Si product content was 19820 ppm. ¹³C and ²⁹Si nuclearmagnetic resonance (NMR) confirmed 6.4 to 6.8 mol % silanefunctionalization. Sample FT-IR of the resultant product is shown inFIG. 16. Sample TGA, DSC, and GPC spectra of Step 2B product areprovided in FIGS. 17, 18, and 19, respectively. Spectra corresponding to¹³C NMR and ²⁹Si NMR for the Step 2B product are also provided in FIGS.20 and 21, respectively.

Example 1.3: Synthesis of Pendant Silane-Containing Resin Via PhenolFunctionalization with Anhydride Silane

The following is an example of the synthesis of asilane-containing/ester modified resin using an acetoxystyrene-modifiedstarting material, as depicted in Scheme 3. In this embodiment, phenolgroups of resins were formed by hydrolysis of acetoxy functions, thenreacted with 3-(triethoxysilyl)propylsuccinic anhydride to provide theformation of ester linkage to form a functionalized resin having theFormula: resin-OCO—CH(CH₂COOH)((CH₂)₃—Si(OCH₂CH₃)₃). Exemplary startingreagent and end product embodiments of this synthetic route are alsodepicted in FIG. 1C.

Step 3A: Synthesis of Pendant Phenol-Functionalized Resin fromAcetoxystyrene Deprotection

In a one-necked, round-bottom flask (RBF), a stir bar and 50.0 g of 3.4mol % acetoxystyrene-containing resin were charged. Tetrahydrofuran (279mL) was added. The solution was stirred. A solution of 1.76 g of sodiumhydroxide was prepared in 9.25 mL of deionized water. When the startingmaterial resin fully dissolved, the solution of sodium hydroxide wasadded. Triethylamine (TEA, 7.43 g) was added, and the RBF was fittedwith a condenser. The solution was heated to reflux for 4 hours. Thereaction was monitored by FT-IR. The reaction was considered completewhen the carbonyl band (1750 cm-1) fully disappeared. Heating wasstopped. The flask was allowed to cool to room temperature. THF wasevaporated. Dichloromethane (DCM, 280 mL) was added to the RBF, and thesolution was stirred vigorously. The solution was then transferred intoa separatory funnel. The organic layer was washed with 2×280 mL ofaqueous HCl (1 mol/L) and then 4×280 mL of DI water. The organic layerwas dried over magnesium sulfate. The solid was filtered, and thefiltrate was kept. The DCM was removed, and the solid product was driedat 30° C. under reduced pressure until constant weight.

Step 3B: Synthesis of Pendant Silane-Functionalized Resin from PhenolModification with Anhydride Silane

In a 100 mL one-necked round bottom flask, a stir bar and 5.00 g of 3.4mol % hydroxystyrene-containing resin (0.0423 mol containing 0.0015 molof hydroxystyrene units) were charged. DCM (42 mL, 0.04 mol/L inhydroxystyrene units) was added. When the reaction solution wastransparent, the solution was flushed with nitrogen. The flask wasfitted with a reflux condenser, and 0.150 g of anhydrous pyridine(0.0019 mol) was added followed by 0.907 g of 3-(triethoxysilyl)propylsuccinic anhydride (0.0030 mol). The reaction continued at 38 to 40° C.for about 46 hours. DCM was removed under reduced pressure. The productwas washed with 50 mL of anhydrous ethanol (twice) and dried underreduced pressure at 30° C. until constant weight. The yield was 2.6 g(48% of the theoretical yield). Sample FT-IR of the resultant product isshown in FIG. 22. Sample TGA and DSC spectra of Step 3B product areprovided in FIGS. 23 and 24, respectively.

Example 1.4: Synthesis of Pendant Silane-Containing Resin Via SuccinicAnhydride Grafting onto Kristalex™ 3085

In this embodiment, styrene or poly(alpha-methyl)styrene (AMS) resinswere reacted with anhydrides, such as succinic anhydride, to create acarboxylic acid moiety onto which the silane moiety is added, asdepicted in Scheme 4. Exemplary starting reagent and end productembodiments of this synthetic route are also depicted in FIG. 1D.

Step 4A: Synthesis of Pendant COOH-Functionalized Resin from GraftingSuccinic Anhydride onto Kristalex™ 3085

A 3-necked, 2 L round-bottom, 2 L flask was fitted with a thermometer, apressure-equalized addition funnel, and a magnetic stirrer and placedunder N₂. Then, 77.5 g of anhydrous AlCl₃ (581.2 mmol) was made into aslurry with 260 mL of DCM and charged into the bottom of theround-bottom flask with stirring. A separate 1 L round-bottom flask wascharged with 100.0 g of Kristalex 3085 (880.4 mmol), 800 mL of DCM, and26.4 g of succinic anhydride (263.8 mmol) under nitrogen andmagnetically stirred until complete dissolution of the solids. Thesolution was transferred into the pressure-equalized addition funnel fordropwise addition. The solution of AlCl₃ and DCM was chilled with anice/NaCl/water bath. The temperature of the reaction mixture wasmaintained between −3 and 5° C. during the slow addition ofresin/anhydride solution (over 160 min). The reaction was allowed tocontinue for 3 hours after the addition was completed, maintaining thetemperature at 0-15° C. Then, 600 mL of aq HCl 2.5 M solution wascautiously added. The two-phase system was stirred at room temperatureovernight. The aqueous phase was discarded. DCM was added to the organicphase to reach a total volume of 1.8 L. The obtained solution wasdivided into two equal portions. Each portion was washed with aqueousHCl 1M (6 times), then with aqueous NaCl 200 g/L (once). The twoportions were combined and dried over anhydrous MgSO₄. The solid wasremoved by filtration over a filter paper. The solvent was removed, andthe product was dried under reduced pressure at room temperature forabout 20 hours. The yellowish solid weighed 90.2 g (71% of thetheoretical yield). Sample FT-IR of the resultant product is shown inFIG. 25. Sample TGA, DSC, and GPC spectra of Step 4A product areprovided in FIGS. 26, 27, and 28, respectively. Acid titration data isprovided below in Table 2.

TABLE 2 Acid Titration of Step 4A Product Trial sample weight ml [OH]Acid # (mg KOH/g) wt % total acid 1 0.0476 10.2 114.34 35.94 2 0.0444 10120.06 37.72 Average = 117.20 mg KOH/g Average = 2.09 mmol acid/g

Step 4B: Synthesis of Pendant Silane-Functionalized Resin from COOHGroup Functionalization

A 3-necked, 1 L round-bottom flask was fitted with a thermometer andcharged with 72.9 g of 27.87 mol %-Carboxyl-Kristalex™-3085 (515.3 mmolcontaining 143.6 mmol of carboxyl units) and 450 mL of DCM with magneticstirring under nitrogen. When the resin was fully dissolved, theround-bottom flask was chilled with an ice/NaCl/water bath. When thetemperature reached 2.5±2.5° C., 15.6 g of ethyl chloroformate (143.8mmol) followed by 14.6 g of TEA (144.3 mmol) were added. The activationtime (formation of mixed anhydride) was 12 min at 5±3° C. Then, 30.3 gof 3-aminopropyltriethoxysilane (136.9 mmol) was charged. The chillingbath was removed, and the reaction was allowed to warm to roomtemperature. The reaction time was about 15 hours at room temperature.Solvent was removed, and the product was dried under reduced pressure atroom temperature overnight. Then, 500 mL of anhydrous diethyl ether wasadded under nitrogen. The mixture was magnetically stirred untilcomplete dissolution of the resin versus the insoluble byproduct(triethylamine hydrochloride). The byproduct was removed by gravimetricfiltration over Whatman® #1 filter paper. Dry N₂ was bubbled through thefiltrate to evaporate most of the ether. The product was dried underreduced pressure at room temperature overnight. The waxy product weighed92.2 g (90% of the theoretical yield). ICP measured value for Si was35700 ppm. ²⁹Si and ¹³C NMR images indicated 13 to 21 mol %functionalization. Sample FT-IR of the resultant product is shown inFIG. 29. Sample TGA, DSC, and GPC spectra of Step 4B product areprovided in FIGS. 30, 31, and 32, respectively. Spectra corresponding to¹H NMR, ¹³C NMR, and ²⁹Si NMR for the Step 4B product are also providedin FIGS. 33, 34, and 35, respectively.

Example 1.5: Synthesis of Pendant Silane-Containing Resin Via FreeRadical Copolymerization

In this embodiment, the synthesis of functionalized resin proceeds froman earlier starting point, where the resin polymer monomers are reactedwith silane moieties directly to form functionalized resin in one step,as depicted in Scheme 5. Exemplary starting reagent and end productembodiments of this synthetic route are also depicted in FIG. 1E.

Step 5A: Synthesis of Pendant Silane-Functionalized Resin from FreeRadical Copolymerization with Methacrylate Silane

To a 500 mL three-necked round-bottom flask equipped with an overheadpaddle-blade stirrer, thermocouple probe, water-cooled reflux condenser,and 250 mL addition funnel was charged 200 mL reagent-grade toluene, 2 gvinylsilane, 160 g styrene and 60 g 2,4-diphenyl-4-methyl-1-pentene(Sigma-Aldrich, St. Louis, Mo., US) as the chain transfer agent (CTA)and the charge stirred for 20 minutes. To this mixture was then added 40g 3-(trimethoxysilyl) propylmethacrylate (CAS #2530-85-0) and the entiremixture heated to 80° C. while applying a slow nitrogen sparge topreserve an inert atmosphere.

To the addition funnel was charged a solution of 4 gazobisisobutyronitrile (AIBN) dissolved in 100 mL 50/50 ethylacetate/toluene and then added over about 4 hours to the reactionmixture while maintaining the nitrogen sparge and the reactiontemperature of 80° C. This condition was held for a further 4 hoursbefore the mixture was allowed to cool and the reactor contentsdischarged to a wiped-film evaporator apparatus. Solvent, CTA, and anyunreacted monomers were then removed under reduced pressure of about 2torr at a temperature of up to about 200° C. The product was a stickysolid containing some residual CTA and having a molecular weight(gas-phase chromatography (GPC), right, polystyrene standards, FIG. 36)of 900 (M_(n)), 3,530 (M_(w)), and 7,140 (M_(z)).

The nuclear magnetic resonance spectrum (FIG. 37) was generallyconsistent with a polystyrene structure and exhibited a strong broadpeak at about 3.55 ppm for the (trimethoxy)silyl moiety whose integratedarea was also consistent with the amount charged, indicting essentiallycomplete incorporation of the silicon-bearing monomer into the polymerchain.

Example 1.6: Synthesis of End-Capped Silane-Containing Resin Via PhenolFunctionalization Through Succinic Anhydride

In this embodiment, the synthesis of functionalized resin proceeds byphenol functionalization using succinic anhydride to form an end-cappedderivative, as depicted in Scheme 6. Exemplary starting reagent and endproduct embodiments of this synthetic route are also depicted in FIG.1G.

To a 1L round bottom flask fitted with a stir-bar and a reflux condenserwere charged phenol-functionalized resin (56.7 g; containing 38.4 mmolof phenol unit), anhydrous MTBE (380 mL), and triethylamine (5.4 mL;38.74 mmol). The mixture was stirred under N₂ blanket. When the resinwas fully dissolved, succinic anhydride (3.85 g; 38.47 mmol) was addedat once. The flask was heated to 57° C. (oil bath) for 17 hours, thenroom temperature for one half hour. The mixture was then chilled with anice-water-NaCl bath. Ethyl chloroformate (3.7 mL; 38.7 mmol) was addedover 4 min. The activation time was 30 min. 3-Aminopropyltriethoxysilane(9.0 mL; 38.5 mmol) was charged and the chilling bath was removed. Thereaction time (amide formation) was 6 hours at room temperature. Thesolid byproduct was removed by filtration. The volatiles were strippedunder reduced pressure and the residue was dried under vacuum at roomtemperature for 3 days. The resulting white powder product weighed 58.2g (85% of the theoretical). Spectrographs including IR, TGA, DSC, andGPC are set forth in FIGS. 38 to 41, respectively.

Example 1.7: Synthesis of End-Capped Silane-Containing Resin Via PhenolFunctionalization with Chloro-Silane

In this embodiment, the synthesis of functionalized resin proceeds inthis embodiment by (3-chloropropy)triethoxysilane reaction with sodiumethoxide, sodium iodide, and acetone to yield the end-capped silanederivative, as depicted in Scheme 7. Exemplary starting reagent and endproduct embodiments of this synthetic route are also depicted in FIG.1H.

In a 3-neck round bottom flask fitted with a thermometer, overheadstirrer, and nitrogen atmosphere were charged 3 g phenol-functionalizedresin (0.677 mmol phenol per 1 gram of resin) and 6 mL acetone (driedover magnesium sulfate). The reaction mixture was placed under anitrogen blanket and agitated with a mechanical overhead stirrer. Thereaction mixture was heated to 20 to 25° C. to dissolve the resin. Afterdissolving the resin in acetone, sodium ethoxide (0.191 g) was added tothe reaction mixture and stirred for 15 minutes. Subsequently sodiumiodide (0.42 g) was added at 45 to 50° C. Then(3-chloropropy)triethoxysilane (0.848 g) was added and the reactiontemperature adjusted to 55° C. The reaction mixture was stirred for 24hours at 55° C. After 24 hours reaction time, n-heptane was added to thereaction mixture to precipitate salts. The salts were removed viafiltration on a Buchner funnel by filtering through a Celite pad. Thereaction mixture was stripped using a Rotary evaporator. The amorphousproduct weighed 3.1 g (88% of theory). The end-product was analyzed by²⁹Si NMR yielding the graph provided in FIG. 42.

Example 1.8: Synthesis of Pendant Silane-Containing Resin ViaCopolymerization of Isobornylmethacrylate and3-(Trimethoxysilyl)Propylmethacrylate

In this embodiment, the synthesis of pendant functionalized resin inthis embodiment is achieved by reaction of isobornylmethacrylate with3-(trimethoxysilyl) propylmethacrylate under the conditions set forth inScheme 8. Exemplary starting reagent and end product embodiments of thissynthetic route are also depicted in FIG. 1I.

A 1L 3-necked round-bottom flask equipped with nitrogen inlet, overheadstirrer, thermocouple probe, reflux condenser, and port fitted with a500 mL addition funnel was charged with 250 mL butylbutyrate processsolvent. The addition funnel was charged with a solution of 16 g LuperoxDI (di-tert-butylperoxide, 8 wt % on total monomers), 40 g3-(trimethoxysilyl)propylmethacrylate (20 wt % or 18.3% molar on totalmonomers), 160 g isobornylmethacrylate, and 50 mL butylbutyrate. Thereactor was heated under a gentle stream of nitrogen with agitation to153° C. and held at this temperature for the course of the reaction. Themonomers and initiator solution was then added slowly, dropwise, to thereactor, over 2 hours. After addition was completed, the reactionmixture was held at 153° C. an additional 3 hours then cooled to roomtemperature under a continued gentle stream of nitrogen. Product polymeris obtained by stripping the solvent under vacuum up to about 200° C.Appearance: Slightly hazy, water-white amorphous solid. The ¹H-NMRspectra of the end product provided in FIG. 43 exhibits a prominentsinglet for the trimethoxysilyl functionality at 3.57 ppm, where molarloading calculated from its integration (vs. area of all aliphaticprotons) is ˜17% (vs. 18.3% charged). GPC analysis provides a molecularweight, GPC vs. polystyrene standards, of Mn 900/Mw 1,280/Mz 2,220/MWDof 1.42. The glass transition temperature (Tg) determined by DSC was 8°C., as shown in FIG. 44. FIG. 45 provides the ²⁹Si-NMR data, yielding1.87% Si (theoretical Si level was 2.26%). FIG. 46 sets forth the IRspectrum of the product. ICP analysis of the product indicated an Silevel of 1.59%.

Example 1.9: Synthesis of End-Capped Silane-Containing Resin Via PhenolFunctionalization with Glycidoxy Silane

In this embodiment, the synthesis of end-capped functionalized resin isachieved by PPh₃ reaction with glycidoxypropyltriethoxysilane, asdepicted in Scheme 9. Exemplary starting reagent and end productembodiments of this synthetic route are also depicted in FIG. 1J.

To a 3-neck, 500 mL round bottom flask equipped with a magnetic stir barand a reflux condenser with N₂ gas overflow was charged 150 g ofphenol-functionalized resin (0.677 mmol phenol per 1 gram of resin). Theresin was heated to 160° C. using a silicon oil bath. Then 1.5 gtriphenylphosphine was added to the flask. After complete dissolution,27.5 g of 3-glycidoxypropyltriethoxysilane was added to the flask usinga syringe. The reaction mixture was then stirred for 6 hours at 160° C.The reaction mixture was thereafter cooled to room temperature. Thecrude product was dissolved in methyl ethyl ketone and then precipitatedinto methanol. The precipitated solid was collected and then dried underreduced pressure with N₂ purge at 80° C. Sample TGA (FIG. 47) and DSC(FIG. 48) spectra of the product are provided. Analysis by ¹H-NMR of theproduct is set forth in FIG. 49. FIG. 50 provides the GPC chromatogramand distribution curve of the end product.

Example 1.10: Synthesis of End-Capped Silane-Containing Resin Via AcidFunctionalization with Glycidoxy Silane

In this embodiment, the synthesis of end-capped functionalized resinproceeded by use of an acid-functionalized hydrocarbon resin incubatedwith 3-glycidoxypropyltriethoxysilane, as depicted in Scheme 10.Exemplary starting reagent and end product embodiments of this syntheticroute are also depicted in FIG. 1K.

To a 100 mL round bottom flask was charged 10 g of anacid-functionalized hydrocarbon resin (0.31 mmol of acid function perone gram of resin). The resin was heated to 160° C. in an oil bath withmagnetic stirring under N₂ gas. To this was added 1.84 g of3-glycidoxypropyltriethoxysilane in one portion. This mixture was thenstirred at 160° C. under nitrogen for six hours before it was cooleddown to room temperature to afford the described product. The crudeproduct was dissolved in methyl ethyl ketone and then precipitated intomethanol. The precipitated solid was collected and then dried underreduced pressure with N₂ purge at 80° C. Analyses of the end-product byGPC, ¹H-NMR, TGA are provided in FIGS. 51 to 53, respectively.

Example 1.11: Synthesis of End-Capped Silane-Containing Resin Via PhenolFunctionalization with Glycidoxy Silane

In this embodiment, the synthesis of end-capped functionalized resin wasachieved by incubation of 3-glycidoxypropyltriethoxysilane andacid-modified resin with triphenylphosphine, as depicted in Scheme 11.Exemplary starting reagent and end product embodiments of this syntheticroute are also depicted in FIG. 1L.

Into a 3-neck, 500 mL round bottom flask equipped with a magnetic stirbar, reflux condenser, and septum was added 60 grams of an acid modifiedresin (acid number 53 mg KOH/g) under an N₂ blanket. The resin then washeated to 180° C. after which 0.3 g triphenylphosphine was added to theflask. Upon complete dissolution, 15.76 g of3-glycidoxypropyltriethoxysilane was added to the flask in one portion.This mixture was then stirred at 180° C. under nitrogen for six hoursbefore it was cooled down to room temperature. The crude product wasdissolved in methyl ethyl ketone then precipitated into methanol. Theprecipitated solid was collected then dried under reduced pressure withN₂ purge at 80° C. FIGS. 54 to 57 provide DSC, GPC, ¹H-NMR, and TGAanalysis of the end product, respectively.

Example 1.12: Synthesis of End-Capped Silane-Containing Resin Via PhenolFunctionalization with Phthalic Anhydride and Glycidoxy Silane

In this embodiment, the synthesis of functionalized resin is performedby incubation of the functionalization unit with phthalic anhydride and3-glycidoxypropyltriethoxysilane to create an end-capped functionalizedresin, as depicted in Scheme 12. Exemplary starting reagent and endproduct embodiments of this synthetic route are also depicted in FIG.1M.

To a 100 mL round bottom flask equipped with a magnetic stir bar wascharged 10 g of phenol-functionalized resin (0.677 mmol phenol per 1gram of resin). The resin was heated to 160° C. using a silicon oilbath. P-toluenesulfonic acid, 0.074 g, was then added to the flask.After 15 min, 0.98 g phthalic anhydride was added to the flask. Themixture was stirred for 2 hours at 160° C. followed by addition of 0.1 gtriphenylphosphine and 1.84 g 3-glycidoxypropyltriethoxysilane. Themixture was then stirred for an additional 4 hours before it was cooledto room temperature. The crude product was dissolved in methyl ethylketone and then precipitated into methanol. The precipitated solid wascollected and then dried under reduced pressure with N₂ purge at 80° C.The end-product analyzed by ¹H-NMR is provided in FIG. 58. The GPCchromatogram and distribution curve of the end-product is shown in FIG.59.

The above methods described in Examples 1.1 to 1.12 yield variousfunctionalized resin compositions obtained through different routes ofsynthesis. Each route can be varied according to known procedures toyield resins possessing different properties, i.e. different degrees offunctionalization, different molecular weights, different Tg values,etc. While many hundreds of such samples were made, provided in Table 3are chemical and physical properties of several examples of silaneresins functionalized by modification of polar linkers synthesized asdescribed the above in Examples 1.1 to 1.5

TABLE 3 Exemplary Properties of Functionalized Resins Silane SilaneSilane Silane via ¹³C via ¹³C via ¹³C via Measured NMR NMR NMR- ²⁹Si Sivia ICP Si—CH₂— amide Si—(O—CH₂—CH₃)₃ NMR Sample or XRF (mol (mol (mol(mol Type M_(n) M_(w) M_(z) PDI T_(g) (ppm) %) %) %) %) 1 688 5499 245235.45 16  273 — — — — 1 740 1209 2316 1.63 36  5500 — — — — 2 629 7871083 1.25 34  9590* — — — — 2 642 772 927 1.20 −5 19820 — 6.8 6.4 6.7 2688 902 1706 1.31 −5 26500 — 5.7 7.2 6.6 3 647 888 1541 1.37 28  394 — —— — 4 534 1133 2439 2.12 −7 16200 7.7 5.9 6.4 6.4 4 733 1452 2699 1.98−13 29000 18 19 12 12 4 816 2019 5282 2.47 −7 35700 21 27 15 13 2 9322065 3988 2.22 32  8440 1.4 — 1.7 1.5 2 920 2064 4009 2.24 30  5910 4.42.7 4.5 4.0 6 761 1086 1822 1.43 25  9550 — — — — 7 698 967 1624 1.3930400 — — — — 8 900 1280 2220 1.42 8 15900 — — — 1.87 9 743 1168 22621.57 21 10500 — — — — 10 862 1905 4635 2.21 11000 — — — — 11 979 18094903 1.85 16 14200 — — — — 12 695 1234 3190 1.78 12700 — — — — *X-RayFluorescence (XRF) determined value; all other values determined by ICPSample Type: 1 = acetoxy pendant route 2 = phenol end-capped route 3 =silane anhydride grafting route 4 = succinic anhydride grafting route 5= one pot methacrylate silane copolymerization route 6 = end-cappedester amide route 7 = end-capped phenyl ether route 8 = copolymer ofisobornylmethacrylate and 3-(trimethoxysilyl)propylmethacrylate 9 =glycerol ether route 10 = glycerol ester route 11 = glycerol succinateroute 12 = glycerol ester ether route

Example 2: Analytical Characterization of Functionalized Resins, GeneralMethods

General methods: Analytical analysis was completed on eachsilane-functionalized resin product. IR was used to monitor thereactions. NMR or ICP was used to confirm the presence of silane.Differential scanning calorimetry (DSC) and thermogravimetric analysis(TGA) were used to evaluate thermal stability. GPC was used to determineany molecular weight changes.

Fourier transform-infrared spectroscopy (FT-IR) was conducted using aPerkinElmer® spectrometer with a resolution derived from 8 scans(PerkinElmer, Waltham, Mass., US). The samples were prepared bydissolving about 10 mg of material in 0.1 mL of DCM. One to two drops ofthe obtained solution were placed on an KBr card and dried under N₂ flowfor a few min.

Generally, ²⁹Si and ¹³C NMR analysis involved dissolving resin (100-300mg, depending on sample availability) and chromium(III) acetylacetonate(16 to 36 mg) in 1 mL of deuterated chloroform. The samples were stirredat ambient temperature until all materials were fully dissolved.Hexamethyldisiloxane (40 to 100 microliters) was added to each solutionas an internal standard, and the samples were stirred again briefly. Thesample solutions were then transferred to 5 mm NMR tubes. Spectra wereacquired at 26° C. at 125 or 150 MHz for carbon NMR and 99 or 119 MHzfor silicon NMR. The relaxation delay was 1 to 2 seconds for carbon NMRand 5 seconds for silicon NMR. The number of scans was typically 12500for carbon NMR and 1250 for silicon NMR up to 24000 for carbon NMR and7400 for silicon NMR. Calculations of the functionality level werecompleted using both silicon NMR and carbon NMR. NMR was run on a Bruker500 MHz Avance II NMR spectrometer (Bruker Corp., Billerica, Mass., US),with a ¹H frequency of 500 MHz, a ¹³C frequency of 125 MHz, and a ²⁹Sifrequency of 99 MHz. An Agilent 600 MHz DD2 spectrometer with a ¹Hfrequency of 600 MHz, a ¹³C frequency of 150 MHz, and a ²⁹Si frequencyof 119 MHz also was used for some samples (Agilent Technologies, Inc.,Santa Clara, Calif., US). All samples were run at 26±1° C. unlessspecified.

A standard procedure for ICP included preparation of samples eitherusing a digestion method or an alternative preparation in xylenes or asuitable solvent selected for the sample. For digestion, approximately250 milligrams of sample was weighed into a clean Teflon sample tube.Then, 3 mL of concentrated nitric acid was added to each tube (Tracemetal grade, Fisher Chemical, Whippany, N.J., US). The sample tubes werethen capped and placed in the microwave. Samples were microwave-digestedusing a Ultrawave Single Reaction Chamber Digestion System (Milestone,Inc., Shelton, Conn., US, Table 4). Digestion procedure for microwave islisted below in Table 3. Digested samples were diluted to a volume of 25mL, yielding a final acid concentration of ˜10% HNO₃ (based on nitricacid added and expected consumption of nitric acid during thedigestion). A 1 ppm scandium internal standard was added to each sample.Each sample including the method blanks were then analyzed on aPerkinElmer® Optima 2100 ICP-optical emission spectrometry (OES)instrument (PerkinElmer, Inc., Waltham Mass.) with a cyclonic unbaffledspray chamber and concentric nebulizer. The ICP-OES was calibrated witha matrix matched prepared 1 ppm calibration standard and blank. ICP-OESconditions are provided in Table 5.

TABLE 4 UltraWAVE Sample Preparation Conditions Action Temperature (°C.) Time(min) Ramp 130 15 Hold 130 5 Ramp 240 20 Hold 240 20

TABLE 5 ICP Instrument Conditions ICP RF Power (Watts) 1500 Plasma ArGas Flow (L/min) 18 Auxiliary Ar Gas Flow (L/min) 0.2 Nebulizer Gas Flow(L/min) 0.6 Pump Flow rate mL/Min 1.25

DSC scans were performed under nitrogen on a TA Instruments Q200 orQ2000 Differential Scanning Calorimeter (DSC, TA Instruments, NewCastle, Del., US) equipped with a refrigerated cooling system (RCS-90)both using a heating rate of 20° C./min. Glass transition temperatures(Tg) were calculated and reported from the second heating traces. TGAwas conducted under nitrogen with a TA Instruments Q500Thermogravimetric Analyzer (TA Instruments, New Castle, Del., US) atheating rate of 10° C./min with a nitrogen purge of 50 cc/min.

GPC methodologies were as follows: an Agilent 1100 HPLC (AgilentTechnologies, Inc., Santa Clara, Calif., US) equipped with refractiveindex detector (RID) was used for the GPC analysis. The sample wasprepared by dissolving 25 mg of material in 10 mL of THF and sonicatedfor about 5 min. Then, 10 μL of toluene was added and swirled. A portionof this solution was added to a vial. Run Method: Flow: 1 mL/min,Solvent: THF, Runtime: 26 min, RID Temp: 30° C., Column Temp: 30° C.,Injection: 50 μL, Calibration Material: EasiCal PS-1 (AgilentTechnologies, Inc., Santa Clara, Calif., US, Part Number 2010-0505),Column Type: st Column: GPC Guard Column (Agilent Technologies, Inc.,Santa Clara, Calif., US, Part Number PL1110-1520), Particle Size—5 μm,Length: 50 mm×7.5 mm, 1st Column: PLGel 5 μm MIXED-C, PartNumber—PL1110-6500, Particle Size—5 μm, Length: 300 mm×7.5 mm, 2ndColumn: OligoPore (Agilent Technologies, Inc., Santa Clara, Calif., US,Part Number PL1113-6520), Particle Size—6 μm, Pore Type—100A, Length:300 mm×7.5 mm.

An Agilent 1100 HPLC with an Agilent 1260 Refractive Index detector wasused for GPC analysis (Agilent Technologies, Inc., Santa Clara, Calif.,US). The mobile phase used was tetrahydrofuran stabilized with BHTpreservative (Mollickrodt Pharmaceuticals, Inc., Staines-upon-Thames,England, UK). The stationary phase consisted of three columns fromAgilent: PLgel MIXED guard column (5 micron, 7.5×300 mm, AgilentTechnologies, Inc., Santa Clara, Calif., US), PLgel Mixed C Column (5micron, 7.5×300 mm, Agilent Technologies, Inc., Santa Clara, Calif.,US), and an OligoPore GPC column (5 micron, 7.5×300 mm, AgilentTechnologies, Inc., Santa Clara, Calif., US).

The calibrants used were monodisperse polystyrene standards with amolecular weight (MW) range from 580 to 4,000,000 although peaks forpolystyrene dimer, trimer tetramer, and pentamer, were also observed andincluded in the calibration. Analytical grade toluene was used as flowmarker. A fourth-degree polynomial equation was used to find the bestfit for the Log MW versus the observed retention time. The instrumentparameters used for calibration and sample analysis include a flow rateof 1.0 ml/min, injection volume of 50 microliters while the columns andRI detector were heated at 30° C. Samples were prepared by dissolving 25mg of the sample into 10 ml of THF with BHT, after which 10 microlitersof toluene was added as the flow marker. Samples were analyzed todetermine the Mw, Mn, and Mz of the thermoplastic resins. The percentthermoplastic resin below 300 g/mol and below 600 g/mol, including theamount below 300 g/mol, was determined by GPC integration with AgilentGPC/SEC Software Version 1.2.3182.29519.

The instrument parameters used for calibration and sample analysisinclude a flow rate of 1.0 ml/min, injection volume of 50 microliterswhile the columns and RI detector were heated at 30° C. Samples wereprepared by dissolving 25 mg of the sample into 10 ml of THF with BHT,after which 10 microliters of toluene was added as the flow marker.Samples were analyzed to determine the Mw, Mn, and Mz of thethermoplastic resins.

For acid titration of intermediates, the sample was weighed, and 25 mLof dimethyl formamide (DMF) is added followed by 25 mL of methanol afterdissolution with stirring. The solution was allowed to stir for about 1min, and ten drops of bromothymol blue solution (Fluka Chemie AG, nowSigma-Aldrich, St. Louis, Mo., US), were added. The solution wastitrated using 0.01M sodium methylate in methanol until past equivalencepoint (both visually and using the calculation).

Example 3: Rubber Composition Containing Silane-Functionalized Resin

A functionalized resin with ether linkages to silanol-groups attached tothe backbone of the resin was prepared (10 mol % to 11 mol %functionalized, Resin B) and added to a rubber mixture in amounts of 10phr, 20 phr, and 30 phr to prepare rubber mixtures I1, I2, and I3,respectively, as shown in Table 6 (using styrene-butadiene rubber (SBR))and rubber mixtures I7, I8, and I9, in Table 7 (using natural rubber(NR)). An additional functionalized resin sample, synthesized bysuccinyl linkages to silanol-groups attached to the side groups of theresin, was prepared (27 to 30 mol % functionalized, Resin C) and addedto a rubber mixture in amounts of 10 phr, 20 phr, and 30 phr to preparerubber mixtures I4, I5, and I6, respectively, as also shown in Table 6(SBR) and rubber mixtures I10, I11, and I12 (NR), in Table 7. The rubbermixtures C1 through C6 contained resins without the polar spacer linkerdisclosed herein and the mixture reference did not contain any resin.

TABLE 6 Component* Ref. 1 C1 C2 C3 I1 I2 I3 I4 I5 I6 Rubber^(a) 100 100100 100 100 100 100 100 100 100 Silica^(b) 60 60 60 60 60 60 60 60 60 60Resin a^(c) 0 10 20 30 0 0 0 0 0 0 Resin b^(d) 0 0 0 0 10 20 30 0 0 0Resin c^(e) 0 0 0 0 0 0 0 10 20 30 Anti- 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.02.0 2.0 oxidant^(f) Wax^(g) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0ZnO^(h) 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Fatty acid^(i) 2.5 2.52.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Silane 4.32 4.32 4.32 4.32 4.32 4.324.32 4.32 4.32 4.32 coupling agent^(j) Subtotal 173.32 183.32 193.32203.32 183.32 193.32 203.32 183.32 193.32 203.32 Accelerator^(k) 1.0 1.01.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Vulcanizer^(l) 2.0 2.0 2.0 2.0 2.0 2.02.0 2.0 2.0 2.0 Sulfur^(m) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Total178.32 188.32 198.32 208.32 188.32 198.32 208.32 188.32 198.32 208.32Density 1.16 1.15 1.15 1.14 1.15 1.14 1.13 1.15 1.14 1.13 (g/cm³) *Allamounts in parts per hundred of rubber (phr) unless indicated otherwise^(a)Nipol ® NS 612 (styrene-butadiene rubber (SBR), Zeon Corp.,Tokuyama, Japan) ^(b)Ultrasil ® VN 3GR (Evonik, Wesseling, Germany)^(c)standard resin (Kristalex ™ F-85) ^(d)10% end-capped ether-linkedfunctionalized resin, according to Example 1.2 ^(e)30% pendant succinylfunctionalized resin, according to Example 1.4 ^(f)6PPD(N-(1,3-Dimethylbutyl)-N′-phenyl-p-phenylenediamine) ^(g)Ozone Wax^(h)ZnO ^(i)Stearic Acid ^(j)TESPD-Bis(3Triethoxysilylpropyl)disulfide^(k)DPG (1,3-diphenylguanidine) ^(l)CBS(N-cyclohexyl-2-benzothiazolesulfenamide) ^(m)elemental sulfur

TABLE 7 Component* Ref. 2 C4 C5 C6 I7 I8 I9 I10 I11 I12 Rubber^(a) 100100 100 100 100 100 100 100 100 100 Silica^(b) 60 60 60 60 60 60 60 6060 60 Resin a^(c) 0 10 20 30 0 0 0 0 0 0 Resin b^(d) 0 0 0 0 10 20 30 00 0 Resin c^(e) 0 0 0 0 0 0 0 10 20 30 Anti- 2.0 2.0 2.0 2.0 2.0 2.0 2.02.0 2.0 2.0 oxidant^(f) Wax^(g) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0ZnO^(h) 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Fatty acid^(i) 2.5 2.52.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Silane 4.32 4.32 4.32 4.32 4.32 4.324.32 4.32 4.32 4.32 coupling agent^(j) Subtotal 173.32 183.32 193.32203.32 183.32 193.32 203.32 183.32 193.32 203.32 Accelerator^(k) 1.0 1.01.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Vulcanizer^(l) 2.0 2.0 2.0 2.0 2.0 2.02.0 2.0 2.0 2.0 Sulfur^(m) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Total178.32 188.32 198.32 208.32 188.32 198.32 208.32 188.32 198.32 208.32Density 1.16 1.15 1.15 1.14 1.15 1.14 1.13 1.15 1.14 1.13 [g/cm³] *Allamounts in parts per hundred of rubber (phr) unless indicated otherwise^(a)Natural Rubber (NR) ^(b)Ultrasil ® VN 3GR (Evonik, Wesseling,Germany) ^(c)standard resin (Kristalex ™ F-85) ^(d)10% end-cappedether-linked functionalized resin, according to Example 1.2 ^(e)30%pendant succinyl functionalized resin, according to Example 1.4^(f)Sirantox ® 6PPD (N-(1,3-Dimethylbutyl)-N′-phenyl-p-phenylenediamine)(Jiangsu, Sinorgchem Tech. Co., China) ^(g)Okerin ® OK 2124 (Paramelt B.V., The Netherlands) ^(h)ZnO Rotsiegel Gran (Grillo ZNO GmbH, Goslar,Germany) ^(i)Tefacid RG (straight chain aliphatic monocarboxylic acids,mainly palmitic and stearic acid) (Aarhus Karlshamn, Karlshamn, Sweden)^(j)JH-S75 (Bis[3-(triethoxysilyl)propyl]disulfide) (Jingzhou JianghanFine Chemical, Shashi, Jingzhou, Hubeui, China) ^(k)Denax DPG oil(1,3-diphenylguanidine) (Draslovka A. S., Kolin, Czech Republic)^(l)Vulkacit ® CZ/EG-C (N-cyclohexyl-2-benzothiazolesulfenamide, CBS)(Lanxess GmbH, Cologne, Germany) ^(m)elemental sulfur

Mixture production was performed under industry standard conditions intwo stages in a laboratory 300 mL Brabender mixer with two-wing geometry(CW Brabender GmbH & Co., South Hackensack, N.J., US), as shown in Table8. Test pieces were produced from all of the mixtures by optimalvulcanization under pressure at 160° C. (Table 9), and these test pieceswere used to determine the material properties typical for the rubberindustry by using the test methods given below.

TABLE 8 Mixing for Second Reference Mixture First Mixing Step Rotorspeed (rpm) 70 Starting temperature (° C.) 130 Final temperature (° C.)149 Second Mixing Step Rotor speed 55 Temperature (° C.) 80

TABLE 9 Cure Properties Measurement device MDR 2000 (Alpha TechnologiesServices, LLC, OH, US) Cure Temp. 160° C. Static-Mechanical PropertiesStress-strain analysis In accordance to ISO 37: 2011 Dynamic MechanicalProperties Measurement device Eplexor Temp. 0° C. and 70° C. Strain 10%compression ±0.2% strain amplitude Frequency 10 Hz

The rubber mixtures were tested to determine the resulting tireproperties, as noted in Tables 10 and 11 (results for SBR mixtures andNR mixtures, respectively).

TABLE 10 Ref. 1 C1 C2 C3 I1 I2 I3 I4 I5 I6 Hardness 70.1 65.4 61.1 56.868.8 68.1 66.9 73.2 79.4 78.5 Shore A (RT) Hardness 69.8 64.9 59.5 55.167.6 64.8 62.4 71.5 76.5 75.4 Shore A (70° C.) Resilience 55.6 52.8 4944.6 45.6 40.6 36.6 50.4 42.4 44.2 (RT)/% Resilience 65 65.2 63.6 63.464.2 61.2 55.4 64.6 57.8 58.6 (70° C.)/% Difference^(a)/% 9.4 12.4 14.618.8 18.6 20.6 18.8 14.2 15.4 14.4 T @ tan δ −43 −35 −33 −25 −38 −30 −30−38 −41 −35 (max) temp. sweep/° C. Tg shift/° C. 0 8 10 18 5 13 13 5 2 8tan δ 0.199 0.226 0.272 0.349 0.279 0.318 0.347 0.229 0.269 0.244 (0°C.) at constant strain tan δ 0.089 0.097 0.094 0.096 0.102 0.124 0.1610.11 0.164 0.149 (70° C.) at constant strain ^(a)Difference (resilienceat 70° C.-resilience at room temperature)

TABLE 11 Ref. 2 C4 C5 C6 I7 I8 I9 I10 I11 I12 Hardness 72.0 66.1 63.355.6 71.3 72 69.7 75 78.7 82.9 Shore A (RT) Hardness 70.9 65.6 59.7 5363.8 61.2 55.9 69.6 73 76.3 Shore A (70° C.) Resilience 47.8 42.6 37.434.2 36.8 31.4 27.4 41.6 38 36.4 (RT)/% Resilience 59.8 56.8 55.6 58.253.4 45.6 38.6 56.6 51.6 46.8 (70° C.)/% Difference^(a)/% 12 14.2 18.224 16.6 14.2 11.2 15 13.6 10.4 T @ tan δ −46 −41 −38 −33 −43 −40 −38 −45−42 −42 (max) temp. sweep/° C. Tg shift/° C. 0 5 8 13 3 6 8 1 4 4 tan δ0.183 0.241 0.31 0.363 0.214 0.241 0.271 0.191 0.19 0.198 (0° C.) atconstant strain tan δ 0.131 0.121 0.124 0.133 0.175 0.199 0.251 0.1510.203 0.257 (70° C.) at constant strain ^(a)Difference (resilience at70° C.-resilience at room temperature)

As can be seen from Table 10, Table 11, and FIG. 60, the resinscomprising the functionalized polar linker resolve the conflictingtechnical requirements of an improved wet grip with a low rollingresistance at a higher level. Specifically, the addition of 10 (and 20phr for SSBR) of functionalized resin show an increased value of thedifference of the resilience at 70° C. and the resilience at roomtemperature when compared to the unfunctionalized resin. This differenceis mainly due to a decreased resilience at room temperature as theresilience at 70° C. remains almost unaffected. Moreover, the wet gripis improved as demonstrated by the increased values of tan 6 at 0° C.Nonetheless, the rolling resistance remains largely unaffected, as shownby the very small changes of the values of tan 6 at 70° C. In addition,the Shore A hardness remains almost unaffected by the addition offunctionalized resins or even increases as observed for the highlyfunctionalized resin in compound 14-16 (SBR) and 110-112 (NR). As can beseen from these data, the effects are comparable for both polymersystems.

The inventive resins were also used in a mixture according WO2015153055(the disclosure of which is incorporated herein by references for allpurposes). The observed higher values of tan 6 at 100° C. and 14% strainindicating an improvement in durability, traction and handling at hightemperatures occurring during heavy handling were not observed for theinventive resins given here. In contrast the tan 6 values at 100° C. and14% strain were decreased for the resins when used in compoundingrealized in accordance to WO 2015/153055 (the disclosure of which isincorporated herein by references for all purposes).

Example 4: Ethylene Vinyl Acetate (EVA) Adhesive Compositions ContainingSilane-Functionalized Resins

As noted above, the functionalized resins described herein impart usefuland surprising qualities to a variety of end products and/or end uses.One such end use is adhesive compositions. In this example, two EVAadhesive compositions are prepared and characterized.

Two different adhesive formulations were prepared by thoroughly mixingthe specified polymers, resin, and antioxidants, followed by addition ofthe specified waxes in the ratios shown in Table 12, below (all valuesare in wt %). Example Resin 1.9, which is functionalized as describedherein, and commercial resin Kristalex™ 3085 (Eastman Chemical Company,Kingsport, Tenn., US) were incorporated into adhesive compositions andtested. The formulations were mixed using a mechanical stirrer equippedwith a coil impeller for 15 minutes after additions were complete.Formulations VC1 and VE1 were mixed at 150° C. and applied at 130° C. toa cardboard substrate for testing. Formulations VC2 and VE2 were mixedat 180° C. and applied at 180° C. to cardboard substrates for testing.

TABLE 12 Resin Kristalex ™ Example Kristalex ™ Example 3085 1.9 3085 1.9Adhesive VC1 VE1 VC2 VE2 Evatane ™ 28-800 (wt %) 35 35 0 0 Evatane ™28-40 (wt %) 0 0 19 19 Evatane ™ 28-420 (wt %) 0 0 21 21 Permalyn ™ 6110(wt %) 5 5 0 0 Kristalex ™ 3085 (wt %) 30 0 40 0 Silane-functionalized 030 0 40 Example resin 1.9 (wt %) Paraffin wax (mp 66-69° C.) 29.6 29.6 00 (wt %) Sasolwax ™ 3279 0 0 19.7 19.7 microcrystalline wax (wt %)Irganox ™ 1010 (wt %) 0.4 0.4 0.3 0.3

The adhesives were characterized using the following test methods. TheBrookfield viscosity was tested according to ASTM D3236, “Standard TestMethod for Apparent Viscosity of Hot Melt Adhesives and CoatingMaterials” using a Brookfield DV-II+viscometer with Thermosel™ andspindle 27 at the specified temperature (AMETEK Brookfield,Middleborough, Mass., US). The coefficient of variance was 7%.

Ring and ball softening point (RBSP) was determined according to ASTMD6493-11(2015) “Standard Test Methods for Softening Point of HydrocarbonResins and Rosin Based Resins by Automated Ring-and-Ball Apparatus”using a Herzog 754 apparatus (PAC, L.P., Houston, Tex., US).

Bonded samples for adhesion/fiber tear testing were prepared using hotmelt tester model ASM-15N manufactured by Mitsubishi ElectricCorporation (MEC) in Japan according to Japanese Adhesives Industry(JAI) JAI Method JAI-7-B, with cardboard flutes perpendicular. The fibertear test consists of manually tearing glued cardboard substrates byhand under the specified temperature conditions, and the percent fibertear was visually estimated to the nearest 10%. The glued cardboardsubstrates were conditioned at temperature for at least 10 hours beforetesting. Samples for shear adhesion failure temperature (SAFT) and peeladhesion failure temperature (PAFT) testing were prepared following JAIMethod JAI-7-A, and samples for hold power testing (peel mode) wereprepared following JAI Method JAI-7-C. PAFT and SAFT testing wasconducted with 100 g and 500 g weights, respectively at an oven ramprate of 0.5° C./min. Hold power samples were tested with a 250 g weightat the specified temperature. A minimum of 5 samples were tested foreach test and the average reported. The corrugated cardboard used wasflute type B, 220 g/m² Kraft liner, 220 g/m² Kraft liner (Rengo Co.,Ltd., Japan).

Table 13 provides the formulation test results including viscosity,RBSP, and adhesion results. Compared to adhesive VC1, adhesive VE1containing the silane functionalized resin provides a markedly loweradhesive viscosity. This lower viscosity allows the use of lowerapplication temperature while maintaining fast set time and excellentadhesion down to −15° C. Adhesive VE2, also containing silanefunctionalized resin, significantly increased adhesion to corrugatedcardboard at −7° C. and −15° C. while maintaining comparable SAFTtemperature, viscosity and set times to VC2.

TABLE 13 Resin Kristalex ™ Example Kristalex ™ Example 3085 1.9 3085 1.9Adhesive VC1 VE1 VC2 VE2 Adhesive 76 75 85 85 RBSP (° C.) Viscosity 15301403 7825 8175 at 120° C. (cP) Viscosity at 810 760 4215 4258 140° C.(cP) Viscosity at 467 450 2400 2444 160° C. (cP) open time 8 5 30 30(sec) set time (sec) 6 5 10 10 PAFT (JAI) 55 ± 3 48 ± 3 47 ± 2 37 ± 2SAFT (JAI) 69 ± 3 68 ± 5 62 ± 3 59 ± 8 Hold power at   12 ± 1.4   6 ±1.1   8 ± 0.7   3 ± 0.7 50° C. (JAI peel) (min) Adhesion/Fiber Tear (%)RT 100 100 100 100  −7° C. 100 100 20 100 −15° C. 80 80 10 70

Example 5: Hot Melt Pressure Sensitive Adhesive Compositions ContainingSilane-Functionalized Resin

Styrene-isoprene-styrene (SIS)-based Hot Melt Pressure SensitiveAdhesive (PSA) compositions comprising Piccotac™ 1095 (Eastman ChemicalCompany, Kingsport, Tenn., US) as a tackifying resin were prepared withsilane-functionalized Example Resin 1.9 (above) and with commerciallyavailable Kristalex™ 3085 (Eastman Chemical Company, Kingsport, Tenn.,US) as end-block modifying resins. A reference PSA was similarlyprepared without end-block modifying resin. The composition componentsare provided in Table 14.

TABLE 14 Refer- Kristalex ™ Example ence 3085 Resin 1.9 PSA Component %% % Kraton ™ D1161 41.5 41.5 45.3 Piccotac ™ 1095 45.6 45.6 49.7Kristalex ™ 3085 8.3 0 0 Example Resin 1.9 0 8.3 0 Calsol ™ 5550 oil 4.14.1 4.5 Irganox ™ 1010 0.4 0.4 0.5 PSA Tape Properties Temp at Tan-δ max4.4 4.4 2.4 (DMA Tg, ° C.) Value at Tan-δ max 1.9 2.1 1.9 G′ at 25° C.(dyn/cm² × 1.006 0.9446 0.9425 10⁶) DMA 3rd crossover 102 102 108 Temp(° C.) Brookfield Viscosity 195,500 170,300 475,000 140° C., spindle 27,±7% (cP) Brookfield Viscosity 43,650 40,800 92130 160° C. (cP)Brookfield Viscosity 15,300 14,370 25940 180° C. (cP) Loop tack on SS,lbs, 8.2 ± 0.7 8.4 ± 1 8.7 ± 0.6 avg. load 180° peel on SS (lbs/in) 6.6± 0.7 7.8 ± 1 6.4 ± 1.3 40° C. Hold (min, 43 ± 6   46 ± 5 25 ± 7  0.5″ ×0.5″, 1000 g) 70° C. Hold (min, 1″ × 51 ± 15  25 ± 6 0 1″, 1000 g) SAFT(° C., 1″ × 82 ± 3 77 ± 3 82 ± 4 1″, 1000 g)

The formulations were prepared and mixed in a Brabender Plasti-CorderModel DR-2072 using sigma-type mixing blades (C.W. Brabender®Instruments, Inc., S. Hackensack, N.J., US) at 150° C. and 80-100 rpm.The polymer and antioxidant was pre-processed in a full bowl for 10minutes prior to being used in a formulation. The pre-processed polymerand resin were added to the bowl and mixed for 20 minutes. Oil was addeddropwise with mixing for a total mix time of 50 minutes.

The adhesives were coated on 50 μm (2 mil) Mylar film using a hot meltknife coater at 140° C. The coat weights were 26±2 g/m², and coated tapesamples were conditioned in a controlled temperature and humidityclimate (25° C. and 50% RH) overnight before testing as pressuresensitive adhesives.

Loop tack tests were performed on an MTS Criterion Universal TensileTester model C43-104E in accordance with PSTC-16 (MTS SystemsCorporation, Eden Prairie, Minn., US). The crosshead displacement ratewas 5 mm/s. A 25 mm×125 mm loop of tape was used in the experiments. Thefree loop of tape, unrestricted by the grips, was 75 mm long. Themaximum force per unit width of the specimen was recorded. The initialheight, measured from the bottom of the grips to the substrate surface,was 50 mm. The maximum displacement was 44 mm and the dwell time atmaximum displacement was 1 second.

The peel energy or peel force per unit width was measured in accordancewith PSTC 101: Peel Adhesion of Pressure Sensitive Tape Test MethodA—Single-Coated Tapes, Peel Adhesion at 1800 Angle. Rectangular stripsof 25 mm×250 mm (1″×10″) dimensions were tested using a MTS CriterionUniversal Tensile Tester model C43-104E (MTS Systems Corporation, EdenPrairie, Minn., US) at 5 mm/s (12 inch/minute) crosshead displacementrate.

Shear Adhesion Failure Temperature (SAFT) measurement followed PSTC-17Test Method for Shear Adhesion Failure Temperature (SAFT) of PressureSensitive Tape and was measured using a Shear Test Oven equipped with aHigh Temperature Shear Bank Tester (ChemInstruments, Fairfield, Ohio,US). A 25×25 mm (1″×1″) area of tape was adhered to a stainless-steelpanel using one complete pass of a standard 2 kg (4.5 lb) hand roller.Samples were prepared and climatized for 30 minutes at 25° C. and 50%RH, then placed in the oven and a static load of 500 g was suspendedfrom the tape. The oven was equilibrated for 20 minutes at 30° C., andthen the temperature was increased with a heating rate of 0.5°C./minute. The measured time to failure was recorded and converted to afailure temperature in degrees Celsius (° C.). The minimum number ofsamples for SAFT testing was four.

Shear holding power at 40° C. and 70° C. were measured using a ShearTest Oven equipped with a High Temperature Shear Bank Tester(ChemInstruments, Fairfield, Ohio, US). A 12.5×12.5 mm (0.5″×0.5″) or25×25 mm (1″×1″) area of tape was adhered to a stainless-steel panelusing one complete pass of a standard 2 kg (4.5 lb) hand roller. Sampleswere placed in an oven and samples were climatized to 40° C. or 70° C.,respectively. When reaching this temp, the static load of 1000 g wassuspended from the tape. The measured time to failure was recorded. Theminimum number of samples for sheer hold power testing was five.

Although Example Resin 1.9 comprising silane functionalized resinexhibits a Tg significantly lower than the commercial Kristalex™ 3085incorporated into the comparative example, Example Resin 1.9significantly reduced adhesive viscosity and maintained both loop tackand 180° peel adhesion on stainless steel. Surprisingly, Example Resin1.9 provides shear hold time at 40° C. equal to the comparisoncommercial resin that has a higher Tg. This combination of performanceand physical properties allows the formulator to offer improvedprocessing and lower application temperature compared to a comparablePSA using the comparative resin. Alternatively, the formulator canutilize the modified resin to provide a product with lower viscosity andprocessing temperature and improved 180° peel adhesion and hold power at40° C. and at 70° C. compared to the Reference adhesive without an endblock modifying resin.

Example 6: Non-Vulcanized Thermoplastic Elastomer (TPE) Binary BlendsContaining Silane-Functionalized Resin

Thermoplastic elastomer blends were prepared by thoroughly mixingExample Resin 1.9 (above, 20 wt %) and Kraton™ G-1650(styrene-ethylene/butylene-styrene block copolymer, Kraton PerformancePolymers, Kraton Corporation, Houston, Tex., US, 80 wt %). Forcomparison, commercial resin Kristalex® 3115LV (Eastman ChemicalCompany, Kingsport, Tenn., US) was incorporated into the compositioninstead of Example Resin 1.9. The neat, processed polymer was alsoincluded as a reference.

The following test methods were utilized in this example. Compounds wereprepared by mixing in a Brabender PL-2000 equipped with a Prep-Mixer™mixing bowl and roller blades (C.W. Brabender® Instruments, Inc., S.Hackensack, N.J., US) at 220° C. for 15 minutes at 75 rpm. The blendswere formed into plaques (5″×5″×1/8″) and (4″×4″×¼″) by compressionmolding in a heated Carver press at 180° C. and approximately eight tonsof pressure for five minutes. The plaques were tested for percenttransmittance with a Gardner Haze-Gard Plus No. 4725 instrument (BYKAdditives and Instruments, Wesel, Germany) that was calibrated usingBYK-Gardner standards Nos. 4732 and 4733. The films were die cut intotest articles for various physical tests including tear strength,tensile, and compression set. Remaining material was cut up into pelletsized pieces for melt flow rate measurements.

Tensile samples were die-cut and tested in accordance to ASTM D638 (TypeV) and tested on a MTS Criterion Universal Tensile Tester model C43-104E(MTS Systems Corporation, Eden Prairie, Minn., US). Tear samples weredie cut to compliance with ASTM D624 (die C).

Tensile strength, modulus and elongation at break were measured as perASTM D412 using a MTS Criterion Universal Tensile Tester model C43-104E(MTS Systems Corporation, Eden Prairie, Minn., US) at a crosshead speedof 500 mm/min. Tear strength was measured at the same conditionsfollowing ASTM D624. The results of the six tests were averaged.

Melt flow rate was measured in a Ceast melt flow modular instrument at230° C. with a 2.16 kg weight (Instron, Norwood, Mass., US).

For compression set testing, ASTM D395-14 was used. Test specimens wereconditioned to ambient temperature and humidity for 24 hours and thencut from 6 mm thick plaques using a punch style cutter with an innerdiameter of 13 mm. Three samples of each plaque were loaded into a platecompression device with 4.5 mm spacer bars for constant deflection inaccordance to test method B. Samples were then allowed to remain underconstant ambient lab conditions or in a 70° C. oven for 22 hours.Thickness measurements were taken before compression and 30 minutesafter a conditioning phase after being removed from the device. Thecalculated results are reported in accordance to ASTM 395-14.

Hardness testing was done in accordance with ASTM D2240-05. Samples weremeasured from the same 6 mm plaques used for compression testing, butonly before compression samples were cut. A “type B” Shore A durometerwas used along with a very dense lab bench as a base for testing.Measurements were collected and recorded in compliance with ASTMD2240-05.

Table 15 shows the blend test results, showing the surprising increasein tear strength, % modulus, tensile, and decrease in compression set.

TABLE 15 Reference CC Comparison Control Test Resin Example Kristalex ™Resin 1.9 3115LV no resin Tear Strength (lbf/in) 228 ± 18 309 ± 17 142 ±14  50% modulus (psi, ±20) 702 744 259 100% modulus (psi, ±20) 708 743311 200% modulus (psi, ±20) 760 819 338 300% modulus (psi, ±20) 829 911364 Tensile Strength at break - 1715 ± 278 1884 ± 104 615 ± 450 (psi) %elongation 3236 ± 333 3521 ± 201 2195 ± 1184 Young's modulus (ksi) 4.45.3 0.8 Shore A 86 85 68 Shore D 27 27 15 MFR 230° C./2.16 kg (g/10 2.43.3 0.65 min) Compression set at RT % 36 36 42 (±2) Compression set at70° C. 89 94 84 (±2)

As can be seen from Table 15, the TPE blend comprising thesilane-functionalized resin improved room temperature compression set,tear strength, modulus, tensile strength and elongation compared to theneat polymer without the large, unfavorable increase in 70° C.compression set that results when the unmodified resin Kristalex™ 3115LVis used.

All publications, patents and patent applications cited in thisspecification are herein incorporated by reference, and for any and allpurpose, as if each individual publication, patent or patent applicationwere specifically and individually indicated to be incorporated byreference. In the case of inconsistencies, the present disclosure willprevail.

The embodiments described hereinabove are further intended to explainbest modes known of practicing it and to enable others skilled in theart to utilize the disclosure in such, or other, embodiments and withthe various modifications required by the particular applications oruses. Accordingly, the description is not intended to limit it to theform disclosed herein. Also, it is intended that the appended claims beconstrued to include alternative embodiments.

What is claimed is:
 1. A process to produce a silane functionalizedresin having Formula (I):resin-[Z_(k)—X_(n)—R¹—(CH₂)_(m)—Si(R²)_(p)]_(q)  (I) wherein Z is anaromatic group or an aliphatic group, optionally comprising aheteroatom; wherein X is a linker comprising a heteroatom selected fromsulfur, oxygen, nitrogen, a carbonyl group, or a combination thereof;wherein R¹ comprises one or more of an aliphatic and/or aromatic C₁ toC₁₈ and/or a linkage group comprising a heteroatom; wherein each R² isthe same or different and is independently selected from a C₁ to C₁₈alkoxy, aryloxy, alkyl, aryl, or H, or OH, and is optionally branched,and wherein at least one R² is C₁ to C₁₈ alkoxy, aryloxy, or H, or OH;wherein q is an integer from of at least 1; wherein k is an integer of 0or 1; wherein n is an integer from 1 to 10; wherein m is an integer from0 to 10; and, wherein p is 1, 2, or 3; the process comprising: (a)optionally converting a phenol modified resin having Formula (II):resin-Z_(k)—OH  (II) to an acid-modified resin having Formula (III):resin-Z_(k)—X_(n)—COOH  (III) wherein resin, Z, k, X, and n are asdefined above (b) reacting said acid-modified resin of Formula (III)with a silane coupling agent optionally in the presence of an activationagent and optionally in the presence of a catalyst to produce thefunctionalized resin of Formula (I).
 2. The process according to claim1, wherein Step (a) comprises: reacting the phenol modified resin ofFormula (II) with a cyclic acid anhydride of Formula (IV) or a terminalhalogen-substituted straight-chain carboxylic acid of Formula (V)optionally in the presence of a catalyst,

wherein R³ is independently selected from the group consisting of:substituted and unsubstituted, saturated, unsaturated, andpolyunsaturated C₁-C₈ alkyl, substituted and unsubstituted C₆-C₂₀carbocyclic aryl, and substituted and unsubstituted C₄-C₂₀ heterocyclic;wherein the heteroatoms are selected from the group consisting ofsulfur, nitrogen, and oxygen; wherein Y is a halogen atom; and wherein nis an integer from 1-6.
 3. The process according to claim 2, wherein thecyclic acid anhydride of Formula (IV) is selected from the groupconsisting of: malonic anhydride, succinic anhydride, methylsuccinicanhydride, glutaric anhydride, adipic anhydride, pimelic anhydride,phthalic anhydride, trimellitic anhydride, and maleic anhydride.
 4. Theprocess according to claim 1, wherein Step (a), Step (b) or both Step(a) and (b), is performed in no solvent or in an inert solvent.
 5. Theprocess according to claim 4, wherein Step (a), Step (b) or both Step(a) and (b), is performed in an inert solvent selected from one or moreof the group consisting of: a cyclic ether solvent, an acyclic ethersolvent, a ketone solvent, aromatic hydrocarbons, aliphatic saturatedhydrocarbons, aliphatic unsaturated hydrocarbons, alicyclic saturatedhydrocarbons, alicyclic unsaturated hydrocarbons, halogenatedhydrocarbons, and polar aprotic solvents.
 6. The process according toclaim 1, wherein Step (b) is performed by reaction with a silanecoupling agent having Formula (VI)W—(CH₂)_(m)—Si(R²)_(p)  (VI) wherein m, R², and p as defined above;wherein W is independently selected from the group consisting of: amine,diamine, thiol, isocyanate, epoxide, alkene, and halogen.
 7. The processaccording to claim 1, wherein the temperature in Step (a), in Step (b),or in both Step (a) and (b), is in a range of about 0° C. to about 300°C.
 8. The process according to claim 1, wherein the temperature in Step(a), in Step (b), or in both Step (a) and (b), is in a range of about100° C. to about 250° C.
 9. The process according to claim 1, whereinthe temperature at which Step (a), Step (b), or both Step (a) and (b),is performed is in a range of about 150° C. to about 250° C.
 10. Theprocess according to claim 1, wherein the catalyst in Step (a), in Step(b), or in both Step (a) and (b), is selected from one or more of thegroup consisting of: quaternary ammonium salts, quaternary phosphoniumsalts, iodide salts, triphenylphosphine, 4-dimethylaminopyridine,alkaline, Lewis acids, and Bronsted acids.
 11. The process according toclaim 1, wherein the acid modified resin having Formula (III) isobtained by polymerizing or co-polymerizing one or more monomers havinga carboxylic acid functional group.
 12. The process according to claim1, wherein the acid modified resin having Formula (III) is obtained bypolymerization in the presence of a modifier comprising a carboxylicacid functional group.
 13. The process according to claim 12, where themodifier is a free radical initiator or a chain terminator.
 14. Aprocess to produce a silane functionalized resin having Formula (I),resin-[Z_(k)—X_(n)—R¹—(CH₂)_(m)—Si(R²)_(p)]_(q)  (I) which comprises:contacting a phenol modified resin having Formula (II)resin-Z_(k)—OH  (II) with a silane coupling agent having Formula (VI)W—(CH₂)_(m)—Si(R²)_(p)  (VI), optionally in the presence of a catalyst,wherein Z is an aromatic group or an aliphatic group, optionallycomprising a heteroatom; wherein X is a linker comprising a heteroatomselected from sulfur, oxygen, nitrogen, a carbonyl group, or acombination thereof; wherein W is independently selected from the groupconsisting of: amine, diamine, thiol, isocyanate, epoxide, alkene, andhalogen; wherein R¹ comprises one or more of an aliphatic and/oraromatic C₁ to C₁₈ and/or a linkage group comprising a heteroatom;wherein each R² is the same or different and is independently selectedfrom a C₁ to C₁₈ alkoxy, aryloxy, alkyl, aryl, or H, or OH, and isoptionally branched, and wherein at least one R² is C₁ to C₁₈ alkoxy,aryloxy, or H, or OH; wherein q is an integer from of at least 1;wherein k is an integer of 0 or 1; wherein n is an integer from 1 to 10;wherein m is an integer from 0 to 10; and, wherein p is 1, 2, or
 3. 15.The process according to claim 14, wherein: the reaction is performed inno solvent or in an inert solvent, and the solvent is at least oneselected from the group consisting of: a cyclic ether solvent, anacyclic ether solvent, a ketone solvent, aromatic hydrocarbons,aliphatic saturated hydrocarbons, aliphatic unsaturated hydrocarbons,alicyclic saturated hydrocarbons, alicyclic unsaturated hydrocarbons,halogenated hydrocarbons, and polar aprotic solvents.
 16. The processaccording to claim 14, wherein the temperature is in a range of about 0°C. to about 300° C.
 17. The process according to claim 14, wherein thetemperature is in a range of about 100° C. to about 250° C.
 18. Theprocess according to claim 14, wherein the temperature is in a range ofabout 150° C. to about 250° C.
 19. The process according to claim 14,wherein the catalyst is one or more of quaternary ammonium salts,quaternary phosphonium salts, iodide salts, triphenylphosphine,4-dimethylaminopyridine, alkaline, Lewis acids, and Bronsted acids. 20.A polymerization process to produce a silane functionalized resin havingFormula (I),resin-[Z_(k)—X_(n)—R¹—(CH₂)_(m)—Si(R²)_(p)]_(q)  (I) which comprises:heating a mixture of monomers comprising: (i) one or more alkyl, aryl,and/or aralkyl acrylates/methacrylates, (ii) at least onetrialkoxysilyl-functionalized alkyl, aryl, and/or aralkylacrylate/methacrylate, (iii) optionally one or more vinyl ester and/orstyrene or alkyl-substituted styrene, and (iv) optionally an inertsolvent, wherein heating is performed in the presence of a substancethat forms free radicals when heated; wherein the mixture temperature israised sufficiently to cause the substance to decompose and initiateco-polymerization of the monomer mixture; wherein Z is an aromatic groupor an aliphatic group, optionally comprising a heteroatom; wherein X isa linker comprising a heteroatom selected from sulfur, oxygen, nitrogen,a carbonyl group, or a combination thereof, wherein W is independentlyselected from the group consisting of: amine, diamine, thiol,isocyanate, epoxide, alkene, and halogen; wherein R¹ comprises one ormore of an aliphatic and/or aromatic C₁ to C₁₈ and/or a linkage groupcomprising a heteroatom; wherein each R² is the same or different and isindependently selected from a C₁ to C₁₈ alkoxy, aryloxy, alkyl, aryl, orH, or OH, and is optionally branched, and wherein at least one R² is C₁to C₁₈ alkoxy, aryloxy, or H, or OH; wherein q is an integer from of atleast 1; wherein k is an integer of 0 or 1; wherein n is an integer from1 to 10; wherein m is an integer from 0 to 10; and, wherein p is 1, 2,or 3.